Effects of temperature on the release of nutrient elements of solid organic materials under conditions of oversaturation

The effects of temperature on the release of chemical components of six solid organic materials under conditions of oversaturation were investigated in this paper. The six materials were peat moss (PM), weathered coals (WC), charred rice husks (CRH), sawdust (Sd), turfgrass clippings (TC), and chicken manure (CM). Significant differences were observed in the available nitrogen and phosphorus content of the aqueous extracts of organic materials at different temperatures. The available nitrogen content in aqueous extracts of PM and WC at 25 °C was higher than that registered at 15 °C and 35 °C. Available nitrogen content in the aqueous extracts of CRH, Sd, TC, and WC at 35 °C was higher than at 15 °C and 25 °C. The available phosphorus content in the aqueous extracts of organic materials at 35 °C was higher than that available at 15 °C and 25 °C, with the exception of Sd. In addition, the release of available phosphorus in the aqueous solution of organic materials at different temperatures varied constantly for 108 h. The release of potassium (K⁺) and sodium (Na⁺) ions in the aqueous extracts of organic materials was basically steady over time, with the exception of CM. High temperature (35 °C) may significantly hasten the release of K⁺ from organic substrates (except for WC) with low temperatures significantly inhibiting release of K⁺ in Sd and CRH. High temperatures (35 °C) might significantly facilitate the release of Na⁺ in CM and TC. However, no significant differences were manifested in the release of Na⁺ from organic substrates at different temperatures, with the exception of CM and TC. Moreover, no significant differences were observed in the release of calcium, magnesium and iron ions with time, nor were there any significant differences in the contents of iron ions in the aqueous extracts of organic materials at different temperatures. The results indicate that multiple mediums should be pretreated in water for a week before being used for planting. They should be used when all mineral elements of organic materials are steady and ignoring the effect of organic mediums.     

Simulation of substrate degradation in composting of sewage sludge

To simulate the substrate degradation kinetics of the composting process, this paper develops a mathematical model with a first-order reaction assumption and heat/mass balance equations. A pilot-scale composting test with a mixture of sewage sludge and wheat straw was conducted in an insulated reactor. The BVS (biodegradable volatile solids) degradation process, matrix mass, MC (moisture content), DM (dry matter) and VS (volatile solid) were simulated numerically by the model and experimental data. The numerical simulation offered a method for simulating k (the first-order rate constant) and estimating k₂₀ (the first-order rate constant at 20 °C). After comparison with experimental values, the relative error of the simulation value of the mass of the compost at maturity was 0.22%, MC 2.9%, DM 4.9% and VS 5.2%, which mean that the simulation is a good fit. The k of sewage sludge was simulated, and k₂₀, k_20s (first-order rate coefficient of slow fraction of BVS at 20 °C) of the sewage sludge were estimated as 0.082 and 0.015 d^?1, respectively.     

Optimization of thermo-chemical hydrolysis of kitchen wastes

Municipal Solid Wastes (MSWs) in Greece consist mainly of fermentable organic material such as food scraps (～50%) and paper residuals (～20%). The aim of this work was to study the thermo-chemical pretreatment of the kitchen waste (KW) fraction of MSW focusing on biotechnological exploitation of pretreated wastes for biofuel production. A representative sample of municipal food residues was derived by combining weighted amounts of each individual type of residue recognized in daily samples obtained from the University of Patras’ students restaurant located at the Students Residence Hall (Greece). Chemical pretreatment experiments of the representative KW sample were performed using several types of chemical solutions (i.e. H₂SO₄, HCl, NaOH, H₂SO₃) of different solute concentration (0.7%, 1.5%, 3%) at three temperatures (50, 75, 120 °C) and a range of residence times (30–120 min). Optimized results proved that chemical pretreatment of KW, using either 1.12% HCl for 94 min or 1.17% HCl for 86 min (at 100 °C), increased soluble sugars concentration by 120% compared to untreated KW. The increase of soluble sugars was mainly attributed to the mono-sugars glucose and fructose.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

Selection of adsorbents for treatment of leachate: batch studies of simultaneous adsorption of heavy metals

The simultaneous adsorption of copper (Cu), cadmium (Cd), nickel (Ni), and lead (Pb) ions from spiked deionized water and spiked leachate onto natural materials (peat A and B), by-product or waste materials (carbon-containing ash, paper pellets, pine bark, and semi-coke), and synthetic materials (based on urea-formaldehyde resins, called blue and red adsorbents) or mixtures thereof was investigated. The adsorbents that gave the highest metal removal efficiencies were peat A, a mixture of peat B and carbon-containing ash, and a mixture of peat A and blue. At an initial concentration of 5 mg/l for each metal, the removal of each species of metal ion from spiked water and spiked leachate solutions was very good (>90%) and good (>75%), respectively. When the initial concentration of each metal in the solutions was twenty times higher (100 mg/l), there was a noticeable decrease in the removal efficiency of Cu²⁺, Cd²⁺, and Ni²⁺, but not of Pb²⁺. Langmuir monolayer adsorption capacities, q_m, on peat A were found to be 0.57, 0.37, and 0.36 mmol/g for Pb²⁺, Cd²⁺, and Ni²⁺, respectively. The order of metal adsorption capacity on peat A was the same in the case of competitive multimetal adsorption conditions as it was for single-element adsorption, namely Pb²⁺ > Cd²⁺ ≥ Ni²⁺. The results show that peat alone (an inexpensive adsorbent) is a good adsorbent for heavy metal ions.     

Effects of Nitrogen Deposition on Bryophyte Species Composition of Calcareous Grasslands

Regular additions of NH₄NO₃ (35–140 kg N ha⁻¹ yr⁻¹) and (NH₄)₂SO₄ (140 kg N ha⁻¹ yr⁻¹) to a calcareous grassland in northern England over a period of 12 years have resulted in a decline in the frequency of the indigenous bryophyte species and the establishment of non-indigenous calcifuge species, with implications for the structure and composition of this calcareous bryophyte community. The lowest NH₄NO₃ additions of 35 kg N ha⁻¹ yr⁻¹ produced significant declines in frequency of Hypnum cupressiforme, Campylium chrysophyllum, and Calliergon cuspidatum. Significant reductions in frequency at higher NH₄NO₃ application rates were recorded for Pseudoscleropodium purum, Ctenidum molluscum, and Dicranum scoparium. The highest NH₄NO₃ and (NH₄)₂SO₄ additions provided conditions conducive for the establishment of two typical calcifuges – Polytrichum spp. and Campylopus introflexus, respectively. Substrate-surface pH measurements showed a dose-related reduction in pH with increasing NH₄NO₃ deposition rates of 1.6 pH units between the control and highest deposition rate, and a further significant fall in pH, of >1 pH unit, between the NH₄NO₃ and (NH₄)₂SO₄ treatments. These results suggest that indigenous bryophyte composition may be at risk from nitrogen deposition rates of 35 kg N ha⁻¹ yr⁻¹ or less. These effects are of particular concern for rare or endangered species of low frequency.     

Thermogravimetric and XRD study of the effects of chloride salts on the thermal decomposition of mercury compounds

In this paper, the effects of chloride salt (MgCl₂, CaCl₂ or NaCl) addition on the thermal decomposition of five inorganic mercury compounds (HgCl₂, HgS, Hg(NO₃)₂·H₂O, HgO, and HgSO₄) were investigated by thermogravimetric analysis. Mercury-contaminated soil samples collected from Inner Mongolia were used to verify the results. The desorption temperatures of the mercury compounds increased in the following order: HgCl = HgCl₂ < HgS < Hg(NO₃)₂·H₂O < HgO < HgSO₄. Among the chloride salts, MgCl₂ had the greatest effect on thermal desorption of the mercury compounds, with the greatest reduction in the initial temperature of thermal desorption. After MgCl₂ treatment, the mercury removal rates for the soil were 65.67–81.35 % (sample A), 70.74–84.91 % (sample B), and 69.08 % (sample C). The increase in the mercury removal rate for sample C with addition of MgCl₂ was particularly large (34.96–69.08 %). X-Ray diffraction analysis of white crystals from the thermal desorption with MgCl₂ indicated that MgCl₂ promoted conversion of the mercury compounds in the soil to mercury(II) chloride and dimercury dichloride. This transformation is beneficial for applying thermal desorption to remedy mercury-contaminated soils and treat of mercury containing waste.     

Pyrolysis behavior of different type of materials contained in the rejects of packaging waste sorting plants

In this paper rejected streams coming from a waste packaging material recovery facility have been characterized and separated into families of products of similar nature in order to determine the influence of different types of ingredients in the products obtained in the pyrolysis process. The pyrolysis experiments have been carried out in a non-stirred batch 3.5 dm³ reactor, swept with 1 L min^?1 N₂, at 500 °C for 30 min. Pyrolysis liquids are composed of an organic phase and an aqueous phase. The aqueous phase is greater as higher is the cellulosic material content in the sample. The organic phase contains valuable chemicals as styrene, ethylbenzene and toluene, and has high heating value (HHV) (33–40 MJ kg^?1). Therefore they could be used as alternative fuels for heat and power generation and as a source of valuable chemicals. Pyrolysis gases are mainly composed of hydrocarbons but contain high amounts of CO and CO₂; their HHV is in the range of 18–46 MJ kg^?1. The amount of COCO₂ increases, and consequently HHV decreases as higher is the cellulosic content of the waste. Pyrolysis solids are mainly composed of inorganics and char formed in the process. The cellulosic materials lower the quality of the pyrolysis liquids and gases, and increase the production of char.     

Formation and decomposition of tetrafluoroborate ions in the presence of aluminum

The formation and decomposition of tetrafluoroborate ions (BF₄⁻) in H₃BO₃-Al³⁺-F⁻ solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF₄⁻ increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF₄⁻ was stable under neutral and alkaline conditions. Fluoride in the form of BF₄⁻ was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF₄⁻ is proposed whereby fluoroaluminate ions formed by the reaction of BF₄⁻ with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.     

The effects of different mixing intensities during anaerobic digestion of the organic fraction of municipal solid waste

Mixing inside an anaerobic digester is often continuous and is not actively controlled. The selected mixing regime can however affect both gas production and the energy efficiency of the biogas plant. This study aims to evaluate these effects and compare three different mixing regimes, 150 RPM and 25 RPM continuous mixing and minimally intermittent mixing for both digestion of fresh substrate and post-digestion of the organic fraction of municipal solid waste. The results show that a lower mixing intensity leads to a higher biogas production rate and higher total biogas production in both cases. 25 RPM continuous mixing and minimally intermittent mixing resulted in similar biogas production after process stabilization, while 150 RPM continuous mixing resulted in lower production throughout the experiment. The lower gas production at 150 RPM could not be explained by the inhibition of volatile fatty acids. Cumulative biogas production until day 31 was 295 ± 2.9, 317 ± 1.9 and 304 ± 2.8 N ml/g VS added during digestion of fresh feed and 113 ± 1.3, 134 ± 1.1 and 130 ± 2.3 N ml/g VS added during post digestion for the 150 RPM, 25 RPM and minimally mixed intensities respectively. As well as increasing gas production, optimal mixing can improve the energy efficiency of the anaerobic digestion process.     

Utilization of Natural Oils for Decomposition of Polyurethanes

The model polyurethane foam and model compact polyurethane material were prepared and then decomposed by means of natural oils. Castor oil and fish oil based polyol were used in this study. Optimal conditions for the polyurethane decomposition were found. Temperature 250 °C was necessary for efficient polyurethane decomposition by castor oil whereas 200 °C is sufficient in the case of fish oil based polyol. Prepared products have hydroxyl number in the range of 95–168 mg KOH g⁻¹. During the polyurethane decomposition no cleavage of double bonds in the fatty acid chains of castor oil and fish oil based polyol was observed.     

Determination of specific gravity of municipal solid waste

This investigation was conducted to evaluate experimental determination of specific gravity (G_s) of municipal solid waste (MSW). Water pycnometry, typically used for testing soils was adapted for testing MSW using a large flask with 2000 mL capacity and specimens with 100–350 g masses. Tests were conducted on manufactured waste samples prepared using US waste constituent components; fresh wastes obtained prior and subsequent to compaction at an MSW landfill; and wastes obtained from various depths at the same landfill. Factors that influence specific gravity were investigated including waste particle size, compaction, and combined decomposition and stress history. The measured average specific gravities were 1.377 and 1.530 for as-prepared/uncompacted and compacted manufactured wastes, respectively; 1.072 and 1.258 for uncompacted and compacted fresh wastes, respectively; and 2.201 for old wastes. The average organic content and degree of decomposition were 77.2% and 0%, respectively for fresh wastes and 22.8% and 88.3%, respectively for old wastes. The G_s increased with decreasing particle size, compaction, and increasing waste age. For fresh wastes, reductions in particle size and compaction caused occluded intraparticle pores to be exposed and waste particles to be deformed resulting in increases in specific gravity. For old wastes, the high G_s resulted from loss of biodegradable components that have low G_s as well as potential access to previously occluded pores and deformation of particles due to both degradation processes and applied mechanical stresses. The G_s was correlated to the degree of decomposition with a linear relationship. Unlike soils, the G_s for MSW was not unique, but varied in a landfill environment due both to physical/mechanical processes and biochemical processes. Specific gravity testing is recommended to be conducted not only using representative waste composition, but also using representative compaction, stress, and degradation states.     

Influence of leaching conditions for ecotoxicological classification of ash

The Waste Framework Directive (WFD; 2008/98/EC) states that classification of hazardous ecotoxicological properties of wastes (i.e. criteria H-14), should be based on the Community legislation on chemicals (i.e. CLP Regulation 1272/2008). However, harmonizing the waste and chemical classification may involve drastic changes related to choice of leaching tests as compared to e.g. the current European standard for ecotoxic characterization of waste (CEN 14735). The primary aim of the present study was therefore to evaluate the influence of leaching conditions, i.e. pH (inherent pH (～10), and 7), liquid to solid (L/S) ratio (10 and 1000 L/kg) and particle size (<4 mm, <1 mm, and <0.125 mm), for subsequent chemical analysis and ecotoxicity testing in relation to classification of municipal waste incineration bottom ash. The hazard potential, based on either comparisons between element levels in leachate and literature toxicity data or ecotoxicity testing of the leachates, was overall significantly higher at low particle size (<0.125 mm) as compared to particle fractions <1 mm and <4 mm, at pH 10 as compared to pH 7, and at L/S 10 as compared to L/S 1000. These results show that the choice of leaching conditions is crucial for H-14 classification of ash and must be carefully considered in deciding on future guidance procedures in Europe.     

Color analysis of combustion ashes of seawater-soaked wood: estimation of salt concentration

The color of wood ash is normally white, but black color ash was observed when seawater-soaked wood was combusted. In order to check the conditions for generation of black ash, we examined both ashing temperatures from 500 to 800 °C and seawater salt densities for wood soaking. As seawater salt densities rose, the ash color got black at ashing temperatures of 500 and 700 °C. The colors of the ash were analyzed by a spectrophotometer, and color space L* a* b* was measured. The L* value and wood ash yield showed a negative correlation when the ashing temperature was at 600 °C. Salt concentration in wood (SC) was practicably estimated from the L* value (R ² = 0.51) by the approximation formula [SC (%) = 11.82e^?0.038L*]. By scanning electron microscope (SEM) observation, black ash of 600 °C was fully covered by translucent material. It was composed of Na, Mg and Cl by energy dispersive X-ray spectroscopy analysis, and seemed to be crystallized seawater salt. Washed black ash was also observed by SEM, translucent seawater salt was removed and the wood tissue was observed. Black ash was found to be carbonized wood tissue residue, and it was generated when seawater salt exists with a woody biomass.     

Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

The production of elemental sulphur and calcium carbonate (CaCO₃) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H₂S) and CaCO₃. H₂S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO₃; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO₃) which comprised a mixture of two CaCO₃ polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO₃ (69 mass% CaCO₃), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO₃ (i.e. >99 mass% as CaCO₃) or precipitated calcium carbonate (PCC).     

Gasification of the char derived from distillation of granulated scrap tyres

This work reports the effect of pressure on the steam/oxygen gasification at 1000 °C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank.In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34 MJ kg⁻¹. The combustion properties of the char (E_A ≈ 50 kJ mol⁻¹), its temperature of self-heating (≈264 °C), ignition temperature (≈459 °C) and burn-out temperature (≈676 °C) were found to be similar to those of a semi-anthracite.It is observed that the yield, H₂ and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm³ kg_char⁻¹ of syngas was produced, containing 28% v/v of H₂ and CO and with a HHV around 3.7 MJ Nm⁻³. At 1.5 MPa, the syngas yield achieved 4.9 Nm³ kg_char⁻¹ with 30% v/v of H₂-CO and HHV of 4.1 MJ Nm⁻³. Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa.It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.     

Effects of composing on sorption capacity of bagasse-based chars

A fresh bagasse sample (0-month) and two composted bagasse and pig manure mixed samples (1-month and 6-month) were used to produce carbon chars. Sample pyrolysis showed greater carbon char yields were obtained from the compost samples than from the bagasse sample. Fourier transform infrared spectra suggested that the chemical structures of the bagasse sample and the two compost samples were quite different, but that the three carbon chars obtained from those precursors were similar. Among the three pyrolyzed chars, the 0-month bagasse char displayed the largest sorption capacity of 3333 mg kg^?1 for the hydrophilic pollutant phenol, presumably resulting from its greater carbon content and O/C ratio. However, the sorption capacities for the hydrophobic pollutant naphthalene of the tow compost chars (3-month, 2001 mg kg^?1; 6-month, 1667 mg kg^?1) were greater than that of the 0-month bagasse char (1428 mg kg^?1). The results indicate that the compost chars had a greater preferential affinity for naphthalene than that in the bagasse char, suggesting that the compost chars possessed greater hydrophobicity.     

Effect of Sediment Humic Substances on Sorption of Selected Endocrine Disruptors

Characterizing sorption processes is essential to understand the environmental distribution and toxicity potential of endocrine disruptors in terrestrial and aquatic systems. The sorption behaviors of three endocrine disruptors (bisphenol A (BPA), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2)) on sediments were investigated using batch techniques. Samples were taken from some representative reaches in several major Chinese rivers. More attention has been paid to the effect of sediment organic components on the sorption of BPA, E2, and EE2. The results show that the sediment organic carbon-normalized partition coefficients (K _oc (sed)) for three endocrine disruptors are in the order of EE2 > E2 > BPA, which corresponds to the octanol-water partitioning coefficients (logK _ow) of the compounds. Moreover, the K _oc values for humic substances (K _oc (hs)) are comparable with the K _oc (sed) values and highly dependent on the physico-chemical properties of humic substances in sediments. The UV absorptivity at 272 nm (A ₂₇₂), which suggests the abundance of aromatic rings in humic substance structure, correlates well with the K _oc (hs) values. In addition, the infrared spectra of the humic substances extracted from sediments show four strong bands centered at 3,400 cm⁻¹, 1,625 cm⁻¹, 1,390 cm⁻¹, and 1,025 cm⁻¹. The K _oc (hs) values have a positive linear relation with the peak area ratio for peak at 1,025 cm⁻¹ and a negative linear relation with the peak area ratio between peaks at 1,625 cm⁻¹ and 1,025 cm⁻¹. Hence, the hydrogen bonds play a critical role to the sorption of selected endocrine disruptors.     

Optimization of thermo-chemical pretreatment and enzymatic hydrolysis of kitchen wastes

The use of abundant waste materials with high carbohydrate content may contribute substantially to reduction of biofuels production cost. The present study aimed at optimizing the combined effect of thermo-chemical pretreatment and enzymatic hydrolysis of kitchen wastes (KW) for maximizing the production of fermentable soluble sugars. To this end, acid pretreatment of KW samples was performed with hydrochloric acid (0–3% HCl) at 30–100 °C for 0–120 min treatment time. Alternatively, alkaline pretreatment of KW samples was performed with potassium hydroxide solution (0–11%) at constant temperature and time (0 °C and 20 min, respectively). KOH pretreatment at such conditions targets to degrade the resistant starch of KW samples. Both acid and alkaline pretreatments were followed by addition of variable levels of enzyme dosage (0–3.6% v/v α-amylase and 0–3.2% v/v amyloglucosidase-AMG) at constant pH, temperature and time (pH = 5, T = 50 °C and t = 30 min, respectively). Based on our results, glucose concentration increased by ～300% after pretreatment with either acid or KOH in combination with enzymatic hydrolysis (2% HCl, 85 °C, 80 min, 0.1% α-amylase, AMG, and 1% KOH, 0 °C, 20 min, 1.1% α-amylase, 0.4% AMG) compared to raw (untreated) KW. Estimating the different Y_G yields at KW loading of 5%, an increase of 192% and 121% for total soluble monosugars and total soluble sugars, respectively, was succeeded compared to untreated KW. The effect of solids loading on the obtained sugar yields using the optimum conditions for thermo-chemical pretreatment followed by enzymatic hydrolysis was also tested resulting to 27.5% increase of the soluble glucose yield when half of the solids loading (2.5%) was used. A decrease of total soluble sugars yield by 32.2% was observed when solely acid hydrolysis at optimum conditions from our previous study was applied at 30% solids loading.