Biodegradable Polyesters and Polyamides From Difunctionalized Lauric and Coconut Fatty Acids

In this work, a major fatty acid from coconut oil was used as starting material in preparing biodegradable polymers. Thus, polyesters and polyamides from varying proportions of monomers, hydroxy- and amino- derivatives of lauric acid were synthesized. Initially, the derivatives were prepared by regioselective chlorination of lauric acid, in the presence of ferrous ions in strong acid medium. Subsequent hydroxylation and amination procedures yielded the hydroxy- and amino- derivatives of lauric acid. These monomers were polymerized in a reaction tube by simple polycondensation method at 220–230 °C for 6–8 h without catalyst. Molecular weight determination using –COOH by end group titration and gel permeation chromatography (GPC) gave an average molar mass of 3,000–5,000 g mol⁻¹ with n = 15–25 monomer units. Thermal properties such as glass transition (T_g) and decomposition (T_d) temperatures were obtained using differential scanning calorimetry (DSC). The same processes of synthesis and determinations above were applied to coconut fatty acids, derived from saponification of coconut oil, and resulted to very similar conclusions. A quick biodegradation assay against fungus Aspergillus niger UPCC 4219 showed that the polymers prepared are more biodegradable than conventional plastics such as polypropylene, poly(ethyleneterepthalate) and poly(tetrafluoroethylene) but not as biodegradable as cellulosic (newsprint) paper.     

Fabrication and Characterization of PLA/PHBV-Chitin Nanocomposites and Their Foams

This paper examines the effect of biobased chitin nanowhisker fillers on the thermal, rheological, physical, mechanical and morphological properties of biobased polylactic acid (PLA) and PLA/polyhydroxybutyrate-co-valerate (PHBV) blended nanocomposites as well as the physical, mechanical and morphological properties of porous PLA and PLA/PHBV nanocomposite foams. Solid nanocomposites of PLA, PLA/PHBV and chitin nanowhiskers were manufactured through melt blending while porous nanocomposites foams were fabricated through a batch foaming process with the aid of CO₂ as blowing agent. It was found that by incorporating small quantities of chitin nanowhiskers (<2 wt%) the mechanical properties of solid specimens are improved while strength and expandability of the foam can be significantly improved, yielding a homogenously distributed cell morphology with average cell size of 1.5 μm.     

Experimental and numerical calculations of waste R-134a thermal decomposition for energy and fluorine material recovery

Considering the global warming potential of R-134a (C₂H₂F₄) with the substantial generation of this refrigerant as waste material in various industrial sectors, the development of proper thermal destruction method of R-134a is of great practical significance. For this, experiment and numerical calculations have initially made for a tubular-type furnace in order to figure out the basic combustion characteristics of R-134a. A series of experimental investigations for the thermal decomposition of R-134a have been made as a function of wall temperature of tubular furnace and important reacting species such as O₂ and H₂O necessary for the decomposition of C₂H₂F₄ into HF, CO₂ and H₂O. In general, the thermal decomposition of R-134a is successfully made for the condition of temperature above 800 °C with the supply of stoichiometric amount of O₂ and these results are well agreed with numerical prediction. And this information is employed for the simulation of a full-scale, practical incinerator used for the CDM project. For this, numerical investigation has been made for a commercial-scale incinerator using CH₄–air flames for the proper destruction C₂H₂F₄ together with the control of pollutants such as CO and NO. In general, the destruction rate of C₂H₂F₄ appears more than 99.99 % and the generation of CO and NO species appears rather sensitive to the operational condition such as amount of water vapor. The numerical method of HFCs (hydrofluorocarbons) thermal treatment shows high possibility as a viable tool for the proper design and optimal determination of the operational condition for a HFCs incinerator.     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

Fouling and Degradation of Polycarbonate in Seawater: Field and Lab Studies

Biofouling and ensuing microbial mediated degradation of Bisphenol A polycarbonate was studied by immersing the samples in sea water of Bay of Bengal (Chennai, India) for 3 months and also under controlled laboratory conditions with marine mixed microbial consortia for 12 months. A 9% weight loss in the sample was observed after 1 year of incubation under in vitro laboratory conditions. A 5% reduction in number average molecular weight and an additional oligomer with a molecular weight of 930 was observed in the same sample. Contact angle decreased by 11% indicating an increase in the surface hydrophilicity. The specific heat decreased by 44% and glass transition temperature decreased by 3 °C with respect to the control indicating chain scission. Formation of new hydroxyl groups and cleavage of carbonate bonds in polycarbonate suggested biodegradation. About 9 μg mL⁻¹ of Bisphenol A, a monomer of polycarbonate, as well as its oxidized products were detected in the supernatant. The nature of degradation in field and in vitro was different. It was predominantly oxidation in the former and hydrolysis in the later environment. A strain exhibiting hydrolase activity was isolated at the end of the 12 months from the in vitro mixed consortia and was identified, based on biochemical and 16S rDNA tests, as Pseudomonas sp. BP2 (GenBank accession no. EU920674).     

Sources and Variability of Indoor and Outdoor Gaseous Aerosol Precursors (O3, NOx and VOCs)

Measurements of indoor and outdoor aerosol concentrations and their gaseous precursors (O₃, NO and NO₂) as well as volatile organic compounds (VOCs) concentrations were performed at two houses in the Oslo metropolitan area. The variability of the concentration of gaseous compounds was studied in respect to their sources in the indoor and outdoor environments. Domestic heating during the winter and photochemical production during the summer were the main sources for outdoor NOx and O₃. In the indoor environment infiltration of outdoor air, candle burning, smoking and indoor chemical reactions were the main sources affecting their concentrations. The concentrations of VOCs outdoors were enhanced during the summer due to biogenic emissions whereas in the indoor environment their values were affected mostly by emissions from materials used during the recent refurbishing of the houses (>0.4 mg/m³).     

A New and Sound Technology for Biogas from Solid Waste and Biomass

Organic waste, as a main constituent of municipal solid waste, has as well as solid biomass a high potential for biogas generation. Despite the importance of biogas generation from these materials, the availability of large-scale biogas processes lacks behind the demand. A newly developed double-stage solid–liquid biogas process, consisting of an open hydrolysis stage and a fixed-bed methane reactor, allows the biogas production from almost all biodegradable solid waste and renewable resources like maize, grass, sugar cane, etc. Furthermore, residues from industrial processes, like the glycerine waste water from biodiesel production, can also be converted into biogas successfully. Due to the strong separation of hydrolysis and methanation, the process is extremely stable. No malfunction has been detected so far. The open hydrolysis releases CO₂ and allows oxidation of sulfur. Consequently, the biogas has a high methane (>72%) and low H₂S concentration (<100 ppm). Stirrers or other agitation equipment are not necessary; only liquids are pumped. The biogas generation becomes controllable for the first time; thus, the actual generation can be easily adapted to the consumption.     

Furniture wood wastes: Experimental property characterisation and burning tests

Referring to the industrial wood waste category (as dominant in the provincial district of Pesaro-Urbino, Marche Region, Italy), this paper deals with the experimental characterisation and the carrying out of non-controlled burning tests (at lab- and pilot-scale) for selected “raw” and primarily “engineered” (“composite”) wood wastes.The property characterisation has primarily revealed the following aspects: potential influence on moisture content of local weather conditions at outdoor wood waste storage sites; generally, higher ash contents in “engineered” wood wastes as compared with “raw” wood wastes; and relatively high energy content values of “engineered” wood wastes (ranging on the whole from 3675 to 5105 kcal kg⁻¹ for HHV, and from 3304 to 4634 kcal kg⁻¹ for LHV).The smoke qualitative analysis of non-controlled lab-scale burning tests has primarily revealed: the presence of specific organic compounds indicative of incomplete wood combustion; the presence exclusively in “engineered” wood burning tests of pyrroles and amines, as well as the additional presence (as compared with “raw” wood burning) of further phenolic and containing nitrogen compounds; and the potential environmental impact of incomplete industrial wood burning on the photochemical smog phenomenon.Finally, non-controlled pilot-scale burning tests have primarily given the following findings: emission presence of carbon monoxide indicative of incomplete wood combustion; higher nitrogen oxide emission values detected in “engineered” wood burning tests as compared with “raw” wood burning test; and considerable generation of the respirable PM₁ fraction during incomplete industrial wood burning.     

Physico-chemical analysis and calorific values of poultry manure

Spain is one of the major producers of broilers and laying hens in the European Union, with an overall market share of around 12%. The poultry manure that is produced is usually employed as fertilizer on cropland, either directly or after a composting process. In some cases, however, this waste is transported over 120 km to be used as fertilizer, with the resulting high transport costs. In other countries, poultry manure is used as an alternative natural fuel source for power generation. In this study, poultry manure from all the laying hen farms in Asturias was characterized with a view to its possible use as an energy source. The Higher Heating Values on a dry basis (experimental) varies between 12,052 and 13,882 kJ/kg. Lower Heating Values (LHVs) on a wet basis range are much lower (mean values of 2664 kJ/kg) due to the high moisture content of poultry manure. Accordingly, the co-combustion of this waste with other types of waste such as forest and wood waste (LHV on a wet basis of 8044 and 15,830 kJ/kg, respectively) or municipal solid waste (LHV on a wet basis of 10,725 kJ/kg) should be considered as an alternative energy source. Chlorine and sulphur contents in dry matter vary around mean values of 0.64% and 0.11%, respectively. The waste also presents high amounts of Ca (4.84%) and K (2.38%).     

Effects of recycled glass substitution on the physical and mechanical properties of clay bricks

In this study, wasted glasses from structural glass walls up to 45 wt.% were added into clay mixtures in brick manufacturing process. Physical and mechanical properties of clay bricks were investigated as functions of the wasted glass content and the firing temperature. The results indicated that with proper amount of wasted glasses and firing temperature, clay bricks with suitable physical and mechanical properties could be obtained. The compressive strength as high as 26–41 MPa and water absorption as low as 2–3% were achieved for bricks containing 15–30 wt.% of glass content and fired at 1100 °C. When the glass waste content was 45 wt.%, apparent porosity and water absorption was rapidly increased.     

Bacteria Degrading PCBs and CBs Isolated from Long-Term PCB Contaminated Soil

Bacteria able to degrade polychlorinated biphenyls (PCBs) and chlorobenzoic acids (CBs) were isolated from soil that had been contaminated with PCBs for 15–30 years. Contaminated soil in which PCB content ranged between 10–470 mg/kg was naturally vegetated with different plants including ash (Fraxinus excelsior), birch (Betula pendula), black locust (Robinia pseudoacacia), Austrian pine (Pinus nigra) and goat willow (Salix caprea) trees as well as a variety of grasses and forbs. Bacteria able to use biphenyl as a sole source of carbon and energy were found in the root zone of all plants, but occurred in the largest numbers beneath pine and black locust. Bacteria able to degrade chlorobenzoic acids were isolated from the same location contaminated with PCBs. Strains that were taxonomically identified by 16S rDNA as Pandoraea were able to use 2-CB, 3-CB, 2,3-CB, 2,5-CB as sole carbon sources, and the strain Arthrobacter utilised 4-CB.     

Reaction mechanism and pathway for the hydrothermal electrolysis of organic compounds

In this study, hydrothermal electrolysis experiments using glucose (a biorelated substance) as a starting material were carried out using a specially designed autoclave at 250°C. We could understand the fundamental reaction behavior of glucose under these conditions through various kinds of experiments and product analyses. Another series of experiments using pressurized CO₂ as an electrolyte was conducted to discover whether it is possible to use CO₂ as an alternative electrolyte to the conventional KCl electrolyte, with a view to lowering the environmental impact of the process. It was found that pressurized CO₂ was useful as an environmentally friendly electrolyte, although there were still some problems in terms of the reaction efficiency.     

Pools and Fluxes of Cations,Anions and Doc in Two Forest Soils Treated With Lime and Ash

The effect of liming and ash treatment on pools, fluxes and concentrations of major solutes was investigated at two forestedsites (Norway spruce) in S. Sweden. One site was treated 15 yrprior to sampling (Hasslöv-Hs; dolomite: 3.45 and 8.75 t ha^-1) and the other 4 yr before (Horröd-Hd; dolomite: 3.25 t ha^-1; wood ash: 4.28 t ha^-1). Effects of limingwere most pronounced in the O horizon solutions where higher pH,elevated Ca (120–700 M) and Mg (50–600 M) were observed as compared to control plots. The impact on the mineralsoil was more moderate. Soil solution concentrations were combined with modelled hydrological flow to calculate mass flows,which largely followed the trends of the solution composition. Liming also resulted in large increases of both exchangeable Caand Mg as well as effective cation exchange capacity (CEC_E;2–5 times the controls). The base saturation (BS%) was raised to 60–100% in the O horizon while in the mineral soil elevated values were only seen at the Hs site (20–60%; down to 10–15 cm depth for 8.75 t ha^-1). Ash treatment did notaffect either the soil solution nor the exchangeable pool to thesame extent as lime. In general, the impact at the Hd site was less pronounced especially in the mineral soil, which might be due to shorter treatment time (4 vs. 15 yr) and also differentthickness of the O horizon. Budget calculations for Ca and Mg originating from the lime showed that a major part of the Ca (40–100%) was retained in the top 30 cm of the soil, of which30–95% was present in the O horizon. The mobility of Mg wasgreater and it was estimated that a significant part had been leached from the profile (30 and 50 cm depth) after 15 yr. Increased mass flows of NO₃ ^- due to nitrification resulting from liming at the Hs site were calculated in the range120–350 mmol m^-2 yr^-1 (or 1.2–3.5 kmol ha^-1 yr^-1). There was significant leaching of Al (25–60 mmol m^-2 yr^-1), of which about 70% was inorganic, in thelower B horizon at both sites with no influence of liming.     

Uptake and Metabolism of TNT and GTN by Plants Expressing Bacterial Pentaerythritol Tetranitrate Reductase

The manufacture and improper disposal of explosives has resulted in a significant amount of land requiring remediation. The compound 2,4,6-trinitrotoluene (TNT) is the most persistent and toxic of the explosive pollutants with current treatment methods being energy intensive and costly. Bacterial enzymes such as pentaerythritol tetranitrate reductase (PETNR) from Enterobacter cloacae PB2 have been found to have activity against TNT; however, microbes often lack the biomassnecessary for remediation applications. The PETNRgene (onr1) was transformed into tobacco plants in an attempt to combine the metabolic diversity of microbes with the sequestering properties of plants. The resulting transgenic plants were shown to have enhanced tolerance to TNT during germination and as seedlings. Phytoremediation applications with these plants may provide an alternative treatment of TNT contamination.     

Enzyme-Mediated Reactions of Oligosaccharides and Polysaccharides

Two types of enzymatic reactions are given here as examples of synthetic problems encountered in industry. In the first case, commercially available -D-galactosidase from Escherichia coli was used as a catalyst to transfer galactose from -lactose to oligosaccharides. A preference for galactosyl transfer to the 3- or 4-position of the sugar moiety of the oligosaccharide was observed for the products. As expected, only the -anomer was produced. A wide variety of sugars, including disaccharides, trisaccharides, cellotetraose, and maltodextrins, has been shown to act as acceptors, yielding oligosaccharides. In the second example, -galactomannan that had been previously treated to contain cationic groups (cationic guar gum) was subjected to treatment with a series of inexpensive commercial enzymes such as lipases, protease, and cellulases. Some enzyme preparations showed significant changes in the viscosities of 1% cationic guar solution. For example, lipases from Aspergillus niger and Aspergillus saitoi and protease XIII from Rhizopus niveus produced a substantial viscosity reduction (0–20% of original viscosity). These examples demonstrate the utility of low-cost enzymes in manipulating polymer structures.     

Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.     

Evaluating the manufacturability and combustion behaviors of sludge-derived fuel briquettes

Based on the physical and chemical properties as well as calorific values of pulp sludge and textile sludge, this study investigates the differences between manufacturability, relationship between extrusion pressure and formability, as well as stability and combustion behaviors of extruded sludge-derived fuel briquettes (ESBB) and cemented sludge-derived fuel blocks (CSBB). The optimum proportion and relevant usage ESBB policies are proposed as well. Experimental results indicate that a large amount of water can be saved during the ESBB manufacturing process. Additionally, energy consumption decreases during the drying process. ESBB also has a more compact structure than that of CSBB, and its mean penetration loading is approximately 18.7 times higher as well. Moreover, the flame temperature of ESBB (624–968 °C) is significantly higher than that of CSBB (393–517 °C). Also, the dry bulk density and moisture regain of ESBB is significantly related to the penetration loading. Furthermore, the optimum mix proportion of ESBB is co-determined by the formability of pulp sludge and the calorific values of textile sludge. While considering the specific conditions (including formability, stability and calorific values), the recommended mix proportion for ESBB is PS50TS50.     

Assessment of mobility and bioavailability of contaminants in MSW incineration ash with aquatic and terrestrial bioassays

Incineration of municipal solid waste (MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction as well as a source of renewable energy. In the process fly and bottom ash is generated as a waste material. The ash residue may vary greatly in composition depending on the type of waste incinerated and it can contain elevated levels of harmful contaminants such as heavy metals. In this study, the ecotoxicity of a weathered, untreated incineration bottom ash was characterized as defined by the H14 criterion of the EU Waste Framework Directive by means of an elemental analysis, leaching tests followed by a chemical analysis and a combination of aquatic and solid-phase bioassays. The experiments were conducted to assess the mobility and bioavailability of ash contaminants. A combination of aquatic and terrestrial bioassays was used to determine potentially adverse acute effects of exposure to the solid ash and aqueous ash leachates. The results from the study showed that the bottom ash from a municipal waste incineration plant in mid-Sweden contained levels of metals such as Cu, Pb and Zn, which exceeded the Swedish EPA limit values for inert wastes. The chemical analysis of the ash leachates showed high concentrations of particularly Cr. The leachate concentration of Cr exceeded the limit value for L/S 10 leaching for inert wastes. Filtration of leachates prior to analysis may have underestimated the leachability of complex-forming metals such as Cu and Pb. The germination test of solid ash and ash leachates using T. repens showed a higher inhibition of seedling emergence of seeds exposed to the solid ash than the seeds exposed to ash leachates. This indicated a relatively low mobility of toxicants from the solid ash into the leachates, although some metals exceeded the L/S 10 leaching limit values for inert wastes. The Microtox® toxicity test showed only a very low toxic response to the ash leachate exposure, while the D. magna immobility test showed a moderately high toxic effect of the ash leachates. Overall, the results from this study showed an ecotoxic effect of the solid MSW bottom ash and the corresponding ash leachates. The material may therefore pose an environmental risk if used in construction applications. However, as the testing of the solid ash was rather limited and the ash leachate showed an unusually high leaching of Cr, further assessments are required in order to conclusively characterize the bottom ash studied herein as hazardous according to the H14 criterion.     

Quality and quantity of sanitary landfill leachate

This paper presents the results of leachate quantity and quality measurement at 20 landfills in the northern part of West Germany over an average period of 3 years. The leachate flow rate could only be estimated as a percentage of annual pre-cipitation (measured precipitation 501–1057 mm year⁻¹). The values for compaction with crawler tractors are 25–50% and with steel wheel compactors, 15–25%. The organic contents of leachate are dependent upon the kind of decomposition conditions (aerobic, anaerobic acetic production or anaerobic methane production). With anaerobic acetic production the volatile fatty acids produced in leachate have a high COD and BOD₅. In the following methane production phase these acids are converted to CO₂ and CH₄ with low organic leachate contents. The concentrations of some inorganic components, such as Fe and Ca, are parallel as a result of changes in pH. Ammonia shows a slow increase with landfill age. In most cases the contents of heavy metals are lower than 1 mg 1⁻¹.     

Pyrolysis of waste animal fats in a fixed-bed reactor: Production and characterization of bio-oil and bio-char

Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.