Above- and below-ground methane fluxes and methanotrophic activity in a landfill-cover soil

Landfills are a major anthropogenic source of the greenhouse gas methane (CH(4)). However, much of the CH(4) produced during the anaerobic degradation of organic waste is consumed by methanotrophic microorganisms during passage through the landfill-cover soil. On a section of a closed landfill near Liestal, Switzerland, we performed experiments to compare CH(4) fluxes obtained by different methods at or above the cover-soil surface with below-ground fluxes, and to link methanotrophic activity to estimates of CH(4) ingress (loading) from the waste body at selected locations. Fluxes of CH(4) into or out of the cover soil were quantified by eddy-covariance and static flux-chamber measurements. In addition, CH(4) concentrations at the soil surface were monitored using a field-portable FID detector. Near-surface CH(4) fluxes and CH(4) loading were estimated from soil-gas concentration profiles in conjunction with radon measurements, and gas push-pull tests (GPPTs) were performed to quantify rates of microbial CH(4) oxidation. Eddy-covariance measurements yielded by far the largest and probably most representative estimates of overall CH(4) emissions from the test section (daily mean up to ～91,500μmolm(-2)d(-1)), whereas flux-chamber measurements and CH(4) concentration profiles indicated that at the majority of locations the cover soil was a net sink for atmospheric CH(4) (uptake up to -380μmolm(-2)d(-1)) during the experimental period. Methane concentration profiles also indicated strong variability in CH(4) loading over short distances in the cover soil, while potential methanotrophic activity derived from GPPTs was high (v(max)～13mmolL(-1)(soil air)h(-1)) at a location with substantial CH(4) loading. Our results provide a basis to assess spatial and temporal variability of CH(4) dynamics in the complex terrain of a landfill-cover soil.     

Action of soil microorganisms on PCL and PHBV blend and films

Poly(hydroxybutyrate-co-valerate) (PHBV) and poly(ε-caprolactone) (PCL) PCL/PHBV (4:1) blend films were prepared by melt-pressing. The biodegradation of the films in response to burial in soil for 30 days was investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG). The PHBV film was the most susceptible to microbial attack, since it was rapidly biodegraded via surface erosion in 15 days and completely degraded in 30 days. The PCL film also degraded but more slowly than PHBV. The degradation of the PCL/PHBV blend occurred in the PHBV phase, inducing changes in the PCL phases (interphase) and resulting in an increase of its crystalline fraction.     

Composition and production rate of pharmaceutical and chemical waste from Xanthi General Hospital in Greece

The objective of this work was to determine the composition and production rates of pharmaceutical and chemical waste produced by Xanthi General Hospital in Greece (XGH). This information is important to design and cost management systems for pharmaceutical and chemical waste, for safety and health considerations and for assessing environmental impact. A total of 233 kg pharmaceutical and 110 kg chemical waste was collected, manually separated and weighed over a period of five working weeks. The total production of pharmaceutical waste comprised 3.9% w/w of the total hazardous medical waste produced by the hospital. Total pharmaceutical waste was classified in three categories, vial waste comprising 51.1%, syringe waste with 11.4% and intravenous therapy (IV) waste with 37.5% w/w of the total. Vial pharmaceutical waste only was further classified in six major categories: antibiotics, digestive system drugs, analgesics, hormones, circulatory system drugs and "other". Production data below are presented as average (standard deviation in parenthesis). The unit production rates for total pharmaceutical waste for the hospital were 12.4 (3.90) g/patient/d and 24.6 (7.48) g/bed/d. The respective unit production rates were: (1) for vial waste 6.4 (1.6) g/patient/d and 13 (2.6) g/bed/d, (2) for syringe waste 1.4 (0.4) g/patient/d and 2.8 (0.8) g/bed/d and (3) for IV waste 4.6 (3.0) g/patient/d and 9.2 (5.9) g/bed/d. Total chemical waste was classified in four categories, chemical reagents comprising 18.2%, solvents with 52.3%, dyes and tracers with 18.2% and solid waste with 11.4% w/w of the total. The total production of chemical waste comprised 1.8% w/w of the total hazardous medical waste produced by the hospital. Thus, the sum of pharmaceutical and chemical waste was 5.7% w/w of the total hazardous medical waste produced by the hospital. The unit production rates for total chemical waste for the hospital were 5.8 (2.2) g/patient/d and 1.1 (0.4) g/exam/d. The respective unit production rates were: (1) for reagents 1.7 (2.4) g/patient/d and 0.3 (0.4) g/examination/d, (2) for solvents 248 (127) g/patient/d and 192 (101) g/examination/d, (3) for dyes and tracers 4.7 (1.4) g/patient/d and 2.5 (0.9) g/examination/d and (4) for solid waste 54 (28) g/patient/d and 42 (22) g/examination/d.     

Functional relationships of landfill and landraise capacity with design and operation parameters.

Solid waste management presses for effective landfill design and operation. While planning and operating a landfill (LF) or a landraise (LR), choices need to be made regarding: (1) LF-LR morphology (base shape, side slopes, final cover thickness, LR/LF height/depth); (2) cell geometry (height, length, slopes); and (3) operation parameters (waste density, working face length, cover thicknesses). These parameters affect LF/LR capacity, operation lifespan and construction/ operation costs. In this paper, relationships are generated between capacity (C, space available for waste) and the above parameters. Incorporating real data into simulation kgamma A1.38, runs, two types of functions are developed: first, C = where A is the LF/LR base area size and kgamma a base shape-dependent coefficient; and second, C = alpha(p,gamma,A) + delta(p,gamma,A)Xp for every parameter p, where Xp is the value of p and alpha(p,gamma,A) and delta(p,gamma,A) are parameter- and base (shape/size)-specific coefficients. Moreover, the relationship between LF depth and LR height that balances excavation volume with cover material, is identified. Another result is that, for a symmetrical combination of LF/LR, with base surface area shape between square and 1:2 orthogonal, and final density between 500 and 800 kg m(-3), waste quantity placed ranges from 1.76A1.38 to 2.55A1.38 tons. The significance of such functions is obvious, as they allow the analyst to investigate alternative LF/LR schemes and make trade-off analyses.     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

Recovery of zinc and lead from fly ash from ash-melting and gasification-melting processes of MSW--comparison and applicability of chemical leaching methods

Fly ash generated from MSW ash-melting and gasification-melting plants, known as Melting Furnace Fly Ash (MFA), contains considerable amounts of heavy metals such as Pb and Zn. These metals can be recovered using a smelting furnace after "pre-treatment" for removal of unnecessary elements such as Cl, Sn and Si. Chemical methods have been studied for pretreatment in the past. However, they have been discussed only with regard to treatment cost and the concentration of Pb and Zn recovered, but neither applicability to various types of MFA nor the environmental impact have been considered. In this study, acid, alkaline and ammonia/chloride leaching methods were compared from the standpoints of: (1) applicability to MFA, (2) concentration of Pb and Zn recovered, (3) treatment cost, and (4) environmental impact. Twenty-three samples of MFAs were collected and classified into 4 types based on element contents. A Pb and Zn recovery experiment was conducted for the representative MFA of those types. The results showed: (1) MFA from gasification-melting plants cannot be treated by chemical methods; (2) the other MFA can be treated to an acceptable quality by existing smelting furnaces; (3) only MFA from electric resistance ash-melting plants can be treated easily by the water washing method; and (4) alkaline and ammonia/chloride leaching methods were more effective than acid leaching.     

Effect of composting process on phytotoxicity and speciation of copper, zinc and lead in sewage sludge and swine manure

The concentration and bioavailability of heavy metals in composted organic wastes have negative environmental impacts following land application. Aerobic composting procedures were conducted to investigate the influences of selected parameters on heavy metal speciation and phytotoxicity. Results showed that both of sewage sludge (SSC) and swine manure (SMC) composting systems decreased the pH, the content of organic matter (OM) and dissolved organic carbon (DOC), and total amounts of Cu, Zn and Pb. Sequential extraction showed that readily extractible fractions of exchangeable and carbonate in Cu and Zn increased during SSC composting but decreased during SMC composting, thus their bioavailability factors (BF) enhanced in SSC but declined in SMC. The fraction of reducible iron and manganese (FeMnOX) of Cu and Zn in SSC and FeMnOX-Cu in SMC decreased, but FeMnOX-Zn in SMC gradually increased in the process of compost. In contrast, the changes of Pb distributions were similar in two organic wastes. Pb was preferentially bound to the residual fraction and its BF decreased. The evolution of heavy metal distributions and BF depended on not only total metal concentrations but also the other properties, such as pH, decomposition of OM and decline of DOC. The germination rate (RSG), root growth (RRG) and germination index (GI) of pakchoi (Brassica Chinensis L.) increased during the composting process. Linear regression analysis demonstrated that GI, which could represent phytotoxic behavior to the plants, could be poorly predicted by BF or total amount of metals, i.e., BF-Zn, T-Cu. However, the inclusion of other physicochemical parameters (pH, OM and DOC) could enhance the linear regression significances (R).     

Stabilization/solidification of fly ashes and concrete production from bottom and circulating ashes produced in a power plant working under mono and co-combustion conditions

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w). Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.     

Biodegradability and Biodegradation of Polyesters

A variety of biodegradable plastics have been developed in order to obtain useful materials that do not cause harm to the environment. Among the biodegradable plastics, aliphatic polyesters such as: poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL), poly(butylene succinate) (PBS), and poly(l-lactide) (PLA) have become the focus of interest because of their inherent biodegradability. However, before their widespread applications, comprehensive studies on the biodegradability and biodegradation mechanisms of these polyesters are necessary. Thus, this paper describes the degradation mechanisms and the effects of various factors on the degradation of polyesters. The distribution of polymer-degrading microorganisms in the environment, different microorganisms and enzymes involved in the degradation of various polyesters are also discussed.     

Methane oxidation in water-spreading and compost biofilters.

This study evaluated two biofilter designs to mitigate methane emissions from landfill vents. Water-spreading biofilters were designed to use the capillarity of coarse sand overlain by a finer sand to increase the active depth for methane oxidation. Compost biofilters consisted of 238-L barrels containing a 1:1 mixture (by volume) of compost to expanded polystyrene pellets. Two replicates of each type of biofilter were tested at an outdoor facility. Gas inflow consisted of an approximately 1:1 mixture (by volume) of CH4 and CO2. Methane output rates (J(out); g m(-2) day(-1)) were measured using the static chamber technique and the Pedersen et al. (2001) diffusion model. Methane oxidation rate (J(ox); g m(-2) day(-1)) and fraction of methane oxidized (f(ox)) were determined by mass balance. For methane inflow rates (J(in)) between 250 and 500 g m(-2) day(-1), the compost biofilter J(ox), 242 g m(-2) day(-1), was not significantly different (P = 0.0647) than the water-spreading biofilter J(ox), 203 g m(-2) day(-1); and the compost f(ox), 69%, was not significantly different (P = 0.7354) than water-spreading f(ox), 63%. The water-spreading biofilter was shown to generally perform as well as the compost biofilter, and it may be easier to implement at a landfill and require less maintenance.     

Guidelines for the evaluation and assessment of the sustainable use of resources and of wastes management at healthcare facilities.

This paper presents guidelines that can be used by managers of healthcare facilities to evaluate and assess the quality of resources and waste management at their facilities and enabling the principles of sustainable development to be addressed. The guidelines include the following key aspects which need to be considered when completing an assessment. They are: (a) general management; (b) social issues; (c) health and safety; (d) energy and water use; (e) purchasing and supply; (f) waste management (responsibility, segregation, storage and packaging); (g) waste transport; (h) recycling and re-use; (i) waste treatment; and (j) final disposal. They identify actions required to achieve a higher level of performance which can readily be applied to any healthcare facility, irrespective of the local level of social, economic and environmental development. The guidelines are presented, and the characteristics of facilities associated with sustainable (level 4) and unsustainable (level 0) healthcare resource and wastes management are outlined. They have been used to assess a major London hospital, and this highlighted a number of deficiencies in current practice, including a lack of control over purchasing and supply, and very low rates of segregation of municipal solid waste from hazardous healthcare waste.     

Injection-Molded Bioblends from Lignin and Biodegradable Polymers: Processing and Performance Evaluation

This paper investigates the effects of the incorporation of lignin and small quantities of epoxidized natural rubber (ENR) as an impact modifying agent on blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL). The addition of lignin resulted in a slight improvement of flexural strength and modulus of the ternary blending system. Incorporation of ENR into the blend resulted in an increase in notched Izod impact strength from 40 to 135% depending on the concentration of ENR. The addition of lignin into the blend resulted in an improvement of thermal stability of the ternary blend system. Morphological analysis showed a good dispersion of PHBV phases and lignin within the PCL matrix. Rheological characterization revealed that the presence of lignin resulted in increased storage modulus of the bioblend.     

Chemical and biological characterization of slaughterhouse wastes compost

The chemical and biological properties of compost made from yard trimmings (YT) composted alone or mixed with slaughterhouse wastes (SHW) were evaluated in seven phases. Mixtures were weighed in a 2:1 proportion (YT:SHW) and placed in composting bins (0.91 m2). Temperature was recorded to determine the time (d) needed to reach the first (1HC) and second heat cycles (2HC). Composting characteristics were measured at 0 d, at the peak of the 1HC and 2HC, and at maturation (0, 20, 50 and 70 d). During 1HC, bacterial isolates were cultivated in both treatments and identified using the Biolog System. Chemical composition was statistically analyzed using a 2 (layers of SHW)x7 (composting phases) factorial arrangement of treatments with the ANOVA procedure of SAS. The pH was neutral for YT and ranged from 7.41 to 6.82 for SHW throughout the process. There was a decrease in organic matter (OM) and carbon (C), and a relative increase in nitrogen (N) in both treatments. At 70 d of maturation, C:N values were similar between treatments, but lower (P>0.05) than the initial values. Final N concentration was higher (P>0.05) for the treatment with SHW. Only the SHW treatment exhibited thermophilic temperatures. At the 1HC in both treatments, different populations of bacteria responsible for the breakdown of OM were identified showing an active heterogeneous population. The presence of pathogenic microorganisms was not detected in treatments containing SHW.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

Processing and Characterization of Recycled Polypropylene and Acrylonitrile Butadiene Rubber Blends

In this paper investigation on thermoplastic elastomers (TPE) and thermoplastic vulcanizates (TPV) derived from waste polypropylene (WPP) of Municipal Solid Waste (MSW) and acrylonitrile-butadiene rubber (NBR) are reported. The WPP was segregated, cleaned, dried and melt processed with NBR at 180 °C in a Brabender Plasticorder at different blend ratios. TPV was prepared by dynamic vulcanization of the TPE with conventional sulfur accelerator curing system. The mechanical properties measured were found to decrease with increase in NBR proportion in the blend; however the dynamic vulcanization of the nitrile rubber phase enhanced the strength properties of the corresponding TPE. The crystallinity of the WPP reduced with increase in NBR ratio. The dynamic modulus decreased with nitrile rubber content in the TPE. Interestingly, the storage modulus of the TPV at higher rubber content enhanced significantly and damping characteristics increased sharply. The rheology studies reveal that the damping of the blend has been reduced with the addition of high storage modulus rubber at melt processing conditions and hence increased viscosity. The amorphous rubber content with higher storage modulus imparts higher viscosity for the polypropylene (PP) matrix at the processing temperature. The SEM study reveals that the dynamic vulcanization of the rubber phase in the blend caused a smoother and finer surface morphology.     

Pyrolysis of virgin and waste polypropylene and its mixtures with waste polyethylene and polystyrene

A comparison of waste and virgin polypropylene (PP) plastics under slow pyrolysis conditions is presented. Moreover, mixtures of waste PP with wastes of polyethylene (PE) and polystyrene (PS) were pyrolyzed under the same operating conditions. Not only the impact of waste on degradation products but also impacts of the variations in the mixing ratio were investigated. The thermogravimetric weight loss curves and their derivatives of virgin and waste PP showed differences due to the impurities which are dirt and food residues. The liquid yield distribution concerning the aliphatic, mono-aromatic and poly-aromatic compounds varies as the ratio of PP waste increases in the waste plastic mixtures. In addition to this, the alkene/alkane ratio of gas products shows variations depending on the mixing ratio of wastes.     

Sample preparation and biomass determination of SRF model mixture using cryogenic milling and the adapted balance method

The biogenic fraction of a simple solid recovered fuel (SRF) mixture (80 wt% printer paper/20 wt% high density polyethylene) is analyzed with the in-house developed adapted balance method (aBM). This fairly new approach is a combination of combustion elemental analysis (CHNS) and a data reconciliation algorithm based on successive linearisation for evaluation of the analysis results. This method shows a great potential as an alternative way to determine the biomass content in SRF. However, the employed analytical technique (CHNS elemental analysis) restricts the probed sample mass to low amounts in the range of a few hundred milligrams. This requires sample comminution to small grain sizes (<200 μm) to generate representative SRF specimen. This is not easily accomplished for certain material mixtures (e.g. SRF with rubber content) by conventional means of sample size reduction.This paper presents a proof of principle investigation of the sample preparation and analysis of an SRF model mixture with the use of cryogenic impact milling (final sample comminution) and the adapted balance method (determination of biomass content). The so derived sample preparation methodology (cutting mills and cryogenic impact milling) shows a better performance in accuracy and precision for the determination of the biomass content than one solely based on cutting mills. The results for the determination of the biogenic fraction are within 1–5% of the data obtained by the reference methods, selective dissolution method (SDM) and ¹⁴C-method (¹⁴C-M).     

Enhanced methane production from ultrasound pre-treated and hygienized dairy cattle slurry

The effect of hygienization (70 °C, 60 min) and ultrasound (6000 ± 500 kJ/kg total solids (TS)) pre-treatments on hydrolysis and biological methane (CH(4)) potential (BMP) of dairy cattle slurry was studied. The BMP of the untreated slurry (control) was 210 ± 10 Nm(3) CH(4)/ton volatile solids (VS) added; after ultrasound pre-treatment it was 250 ± 10 Nm(3) CH(4)/ton VS(added) and after hygienization 280 ± 20 Nm(3) CH(4)/ton VS(added). The specific methanogenic activity (SMA) of the inoculum increased from 22 (untreated) to 26 (ultrasound treated) and up to 28 N ml CH(4)/g VS d, after hygienization. However, only hygienization achieved a positive net energy balance. Both pre-treatments increased the VS-based hydrolysis of slurry (10-96%), soluble nitrogen (N(sol)) content in digestates (20 ± 5%) and biodegradability of the slurry (8 ± 3%) as estimated via elevated VS removal.     

Effect of sewage sludge or compost on the sorption and distribution of copper and cadmium in soil

The application of biosolids such as sewage sludge is a concern, because of the potential release of toxic metals after decomposition of the organic matter. The effect of application of sewage sludge (Sw) and compost (C) to the soil (S) on the Cu and Cd sorption, distribution and the quality of the dissolved organic matter (DOM) in the soil, was investigated under controlled conditions. Visible spectrophotometry, infrared spectroscopy, sorption isotherms (simple and competitive sorption systems), and sequential extraction methods were used. The E4/E6 (lambda at 465 and 665 nm) ratio and the infrared spectra (IR) of DOM showed an aromatic behaviour in compost-soil (C-S); in contrast sewage sludge-soil (Sw-S) showed an aliphatic behaviour. Application of either Sw or C increased the Cu sorption capacity of soil. The Cd sorption decreased only in soil with a competitive metal system. The availability of Cu was low due to its occurrence in the acid soluble fraction (F3). The Cu concentration varied in accordance with the amounts of Cu added. The highest Cd concentration was found in the exchangeable fraction (F2). The Sw and C applications did not increase the Cd availability in the soil.     

Carbon speciation in ash, residual waste and contaminated soil by thermal and chemical analyses

Carbon in waste can occur as inorganic (IC), organic (OC) and elemental carbon (EC) each having distinct chemical properties and possible environmental effects. In this study, carbon speciation was performed using thermogravimetric analysis (TGA), chemical degradation tests and the standard total organic carbon (TOC) measurement procedures in three types of waste materials (bottom ash, residual waste and contaminated soil). Over 50% of the total carbon (TC) in all studied materials (72% in ash and residual waste, and 59% in soil) was biologically non-reactive or EC as determined by thermogravimetric analyses. The speciation of TOC by chemical degradation also showed a presence of a non-degradable C fraction in all materials (60% of TOC in ash, 30% in residual waste and 13% in soil), though in smaller amounts than those determined by TGA. In principle, chemical degradation method can give an indication of the presence of potentially inert C in various waste materials, while TGA is a more precise technique for C speciation, given that waste-specific method adjustments are made. The standard TOC measurement yields exaggerated estimates of organic carbon and may therefore overestimate the potential environmental impacts (e.g. landfill gas generation) of waste materials in a landfill environment.