Determination of MBT-waste reactivity – An infrared spectroscopic and multivariate statistical approach to identify and avoid failures of biological tests

The Austrian Landfill Ordinance provides limit values regarding the reactivity for the disposal of mechanically biologically treated (MBT) waste before landfilling. The potential reactivity determined by biological tests according to the Austrian Standards (OENORM S 2027 1-2) can be underestimated if the microbial community is affected by environmental conditions. New analytical tools have been developed as an alternative to error-prone and time-consuming biological tests. Fourier Transform Infrared (FT-IR) spectroscopy in association with Partial Least Squares Regression (PLS-R) was used to predict the reactivity parameters respiration activity (RA₄) and gas generation sum (GS₂₁) as well as to detect errors resulting from inhibiting effects on biological tests. For this purpose 250 MBT-waste samples from different Austrian MBT-plants were investigated using FT-IR spectroscopy in the mid (MIR) and near infrared (NIR) area and biological tests. Spectroscopic results were compared with those from biological tests. Arising problems caused by interferences of RA₄ and GS₂₁ are discussed. It is shown that FT-IR spectroscopy predicts RA₄ and GS₂₁ reliably to assess stability of MBT-waste materials and to detect errors.     

Scrutinizing compost properties and their impact on methane oxidation efficiency

Methane emissions from active or closed landfills can be reduced by means of microbial methane oxidation enhanced by properly designed landfill covers and engineered biocovers. Composts produced using different waste materials have already been proven to support methane oxidation, and may represent a low-cost alternative to other suitable substrates such as sandy or humic-rich soils, which are frequently not available in sufficient amounts or are too costly. In the present study a data set of 30 different compost materials (different age and input materials) and mixtures, as well as seven soils and mineral substrates were tested to assess methane oxidation rate under similar conditions in a laboratory column set-up. Multivariate data analysis (discriminant analysis) was applied to predict the influence of 21 different parameters (chemical, maturation and physical) on methane oxidation rate in a PLS-DA model. The results show that bulk density, total nutrient content (nitrogen and phosphorus), as well as the quantity and quality (with respect to maturity) of organic matter determined methane oxidation rate in this data set. The model explained 50% of the data variation, indicating how characterisation of oxidation rate by single, even diverse conventional parameters was limited. Thus for the first time, Fourier Transform Infrared (FTIR) spectroscopy was applied to a series of samples to better determine the characteristics of methane-oxidising materials. The initial data obtained in this study appear to be most promising. The prediction of specific methane oxidation rate of a potential biocover material from FTIR spectra and multivariate data analyses is a target to be focused on in the future.     

A Study on Functionalization of Waste Tire Rubber Powder Through Ozonization

In this study, ozone treatment was used to improve the surface wettability of waste tire rubber (WTR) powders. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) were performed in order to characterize the surface composition of the treated samples. The progress of surface modification was also monitored by contact angle measurements of different test liquids (water and liquid paraffin). The surface energy values were evaluated in terms of the Owens’ method and the contact angle data were compared with the results obtained by the surface analytical methods (i.e. FTIR and XPS measurements). These results showed that ozone treatment lead to a remarkable decrease in water contact angle owing to the implantation of oxygen-containing functional groups. Using XPS and FTIR, the oxygen-containing groups can be identified as C–O, O–C=O and C=O. With prolongation of ozone treatment time, WTR exhibited increasing oxygen-containing groups, surface energy and wettability.     

Non-parametric analysis of infrared spectra for recognition of glass and glass ceramic fragments in recycling plants

Glass ceramic detection in glass recycling plants represents a still unsolved problem, as glass ceramic material looks like normal glass and is usually detected only by specialized personnel. The presence of glass-like contaminants inside waste glass products, resulting from both industrial and differentiated urban waste collection, increases process production costs and reduces final product quality. In this paper an innovative approach for glass ceramic recognition, based on the non-parametric analysis of infrared spectra, is proposed and investigated. The work was specifically addressed to the spectral classification of glass and glass ceramic fragments collected in an actual recycling plant from three different production lines: flat glass, colored container-glass and white container-glass. The analyses, carried out in the near and mid-infrared (NIR-MIR) spectral field (1280-4480 nm), show that glass ceramic and glass fragments can be recognized by applying a wavelet transform, with a small classification error. Moreover, a method for selecting only a small subset of relevant wavelength ratios is suggested, allowing the conduct of a fast recognition of the two classes of materials. The results show how the proposed approach can be utilized to develop a classification engine to be integrated inside a hardware and software sorting architecture for fast "on-line" ceramic glass recognition and separation.     

Hazard property classification of waste according to the recent propositions of the EC using different methods

Hazard classification of waste is a necessity, but the hazard properties (named “H” and soon “HP”) are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors.In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>1 0 0).Data for 45 wastes – documented with extensive chemical analysis and flammability test – were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values.This data set showed HP 14 ‘Ecotoxic chronic’ is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 ‘Carcinogenic’. The third most frequent hazard is HP 10 ‘Toxic for reproduction’ and the fourth most frequent hazard is HP 4 “Irritant – skin irritation and eye damage”. In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties.The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.     

Screening tests for hazard classification of complex waste materials – Selection of methods

In this study we describe the development of an alternative methodology for hazard characterization of waste materials. Such an alternative methodology for hazard assessment of complex waste materials is urgently needed, because the lack of a validated instrument leads to arbitrary hazard classification of such complex waste materials. False classification can lead to human and environmental health risks and also has important financial consequences for the waste owner. The Hazardous Waste Directive (HWD) describes the methodology for hazard classification of waste materials. For mirror entries the HWD classification is based upon the hazardous properties (H1–15) of the waste which can be assessed from the hazardous properties of individual identified waste compounds or – if not all compounds are identified – from test results of hazard assessment tests performed on the waste material itself. For the latter the HWD recommends toxicity tests that were initially designed for risk assessment of chemicals in consumer products (pharmaceuticals, cosmetics, biocides, food, etc.). These tests (often using mammals) are not designed nor suitable for the hazard characterization of waste materials. With the present study we want to contribute to the development of an alternative and transparent test strategy for hazard assessment of complex wastes that is in line with the HWD principles for waste classification. It is necessary to cope with this important shortcoming in hazardous waste classification and to demonstrate that alternative methods are available that can be used for hazard assessment of waste materials. Next, by describing the pros and cons of the available methods, and by identifying the needs for additional or further development of test methods, we hope to stimulate research efforts and development in this direction. In this paper we describe promising techniques and argument on the test selection for the pilot study that we have performed on different types of waste materials. Test results are presented in a second paper.As the application of many of the proposed test methods is new in the field of waste management, the principles of the tests are described. The selected tests tackle important hazardous properties but refinement of the test battery is needed to fulfil the a priori conditions.     

Design optimization and standardization of an environmental availability test under both acidic and alkaline conditions

The objective of this study was to design a procedure for an environmental availability test under both acidic and alkaline conditions for solid wastes and recycled materials and products. The procedure was designed on the basis of the Dutch availability test NEN 7371. Bottom ash from a municipal solid waste incinerator and copper slag were used as test materials. The influences of the type and intensity of liquid stirring apparatus and the open area ratio of the top of the leaching vessel were investigated experimentally, and partial least-squares modeling was applied as multivariate data analysis for the simultaneous evaluation of the three leaching conditions. Interlaboratory validation was then carried out with the participation of seven laboratories in accordance with JIS Z 8402-2/ISO 5725-2. Both repeatability and reproducibility were found to be acceptable, but precise calibration of the pH electrode is required. The proposed procedure will provide sufficient accuracy as a standard test method.     

Immobilization of copper ions laden kaolin waste: influence of thermal treatment on its immobilization in cement paste

This work aims to study the influence of thermal treatment of Cu²⁺ laden kaolin wastes on its immobilization efficiency in cement paste. Compressive strength and toxicity characteristic leaching procedure (TCLP) of 5–20 % kaolin waste blended cement pastes were tested. X-ray diffraction (XRD) results illustrate that adsorption of Cu²⁺ ions modify the crystal structure of kaolinite mineral. Fourier transform infrared (FTIR) results indicate that the adsorption sites on the kaolin surface that were occupied with free water molecules have been replaced with Cu²⁺ ions adsorbed from aqueous solutions. The thermal treatment of kaolin waste improves fixation ratio of Cu²⁺ in cement pastes containing up to 20 % of thermally treated waste. This is due to: pozzolanic activity of calcined kaolin, conversion of leachable adsorbed Cu²⁺ ions into encapsulated unleachable phase that does not retard the hydration of cement as well as adsorption of much of leachable Cu²⁺ ions on surfaces of hydration products and occlusion in its lattice structure as illustrated from XRD, FTIR, thermogravimetric, scanning electron microscopy and TCLP results. The fixation ratio of Cu²⁺ in cement paste blended with 20 % of thermally treated kaolin waste, reaches maximum value of about 97 % compared to 82 % for cement paste blended with 20 % of untreated kaolin waste.     

Use of open-path FTIR spectroscopy to address air monitoring needs during site remediations

Although open-path Fourier-transform infrared (FTIR) spectroscopy has been an Environmental Protection Agency (EPA) Toxic Organic Compendium Method since 1996, it has been underutilized as a means to assess exposure to gaseous contaminants during the remediation of hazardous waste sites. This might be considered surprising in light of the many benefits that proper application of this technology can offer. In this article, we provide an overview of the technology and the principle of operation, describe the nature of the data generated, discuss the benefits associated with the technology's use in site clean-up, present emission-rate estimation techniques, and examine the reasons why it has not gained more support over the years. Finally, we present a case study in which the technology was used to drive an 11-month emergency removal action under the direction of the U.S. Environmental Protection Agency.     

Estimating construction and demolition debris generation using a materials flow analysis approach

The magnitude and composition of a region’s construction and demolition (C&D) debris should be understood when developing rules, policies and strategies for managing this segment of the solid waste stream. In the US, several national estimates have been conducted using a weight-per-construction-area approximation; national estimates using alternative procedures such as those used for other segments of the solid waste stream have not been reported for C&D debris. This paper presents an evaluation of a materials flow analysis (MFA) approach for estimating C&D debris generation and composition for a large region (the US). The consumption of construction materials in the US and typical waste factors used for construction materials purchasing were used to estimate the mass of solid waste generated as a result of construction activities. Debris from demolition activities was predicted from various historical construction materials consumption data and estimates of average service lives of the materials. The MFA approach estimated that approximately 610–780 × 10⁶ Mg of C&D debris was generated in 2002. This predicted mass exceeds previous estimates using other C&D debris predictive methodologies and reflects the large waste stream that exists.     

Characterization of ceramic roof tile wastes as pozzolanic admixture

The aim of this work is to study the recycling of tile wastes in the manufacture of blended cements. Cracked or broken ceramic bodies are not accepted as commercial products and, therefore, the unsold waste of the ceramic industry becomes an environment problem. The use of powdered roof tile in cement production, as pozzolanic addition, is reported. The wastes were classified as nonglazed, natural and black glazed tiles. The mineralogy of the powders was controlled by SEM-EDX microscopy, XRD analysis and FTIR spectroscopy. Particle size was checked by laser granulometry. Once the materials were fully characterized, pozzolanic lime consumption tests and Fratini tests were carried out. Different formulations of cement-tile blends were prepared by incorporation of up to 30% weight ratios of recycled waste. The compressive strength of the resulting specimens was measured. The evolution of hydration of the cement-tile blends was analyzed by XRD and FTIR techniques. Vibrational spectroscopy presented accurate evidence of pozzolanic activity. The results of the investigation confirmed the potential use of these waste materials to produce pozzolanic cement.     

Comparison research on waste classification between China and the EU,Japan, and the USA

Waste and waste management have become significant global issues and common challenges that we face. Efficient and effective waste management is an essential part of civilized society. A good waste classification system is the foundation and precondition for efficient waste management. In this paper, in accordance with waste classification principles of systematicness, hierarchy, practical maneuverability and expansibility, waste classification systems in China, the EU, Japan and the USA are reviewed for collection, transportation and treatment sectors. Comparison analysis results show that waste classification methods are diversified and process-oriented classification, substance-oriented and hazardous properties classification principles are widely adopted for waste generation and transportation. For waste treatment process, all the countries and regions adopt similar classification methods based on follow-up treatment process. In general, the EU and Japan all have established their own integrated waste classification system. However, the EU’s macro–micro integration waste classification systems are more suitable for China to learn which process-oriented waste classification is used for declaration and registration at the micro-level and substance-oriented waste classification system for environmental statistics at the macro-level.     

Enhancement of the recycling of waste Ni-Cd and Ni-MH batteries by mechanical treatment

A serious environmental problem was presented by waste batteries resulting from lack of relevant regulations and effective recycling technologies in China. The present work considered the enhancement of waste Ni-Cd and Ni-MH batteries recycling by mechanical treatment. In the process of characterization, two types of waste batteries (Ni-Cd and Ni-MH batteries) were selected and their components were characterized in relation to their elemental chemical compositions. In the process of mechanical separation and recycling, waste Ni-Cd and Ni-MH batteries were processed by a recycling technology without a negative impact on the environment. The technology contained mechanical crushing, size classification, gravity separation, and magnetic separation. The results obtained demonstrated that: (1) Mechanical crushing was an effective process to strip the metallic parts from separators and pastes. High liberation efficiency of the metallic parts from separators and pastes was attained in the crushing process until the fractions reached particle sizes smaller than 2 mm. (2) The classified materials mainly consisted of the fractions with the size of particles between 0.5 and 2 mm after size classification. (3) The metallic concentrates of the samples were improved from around 75% to 90% by gravity separation. More than 90% of the metallic materials were separated into heavy fractions when the particle sizes were larger than 0.5 mm. (4) The size of particles between 0.5 and 2 mm and the rotational speed of the separator between 30 and 60 rpm were suitable for magnetic separation during industrial application, with the recycling efficiency exceeding 95%.     

Preparation of Cellulose Nanocrystals Using an Ionic Liquid

In this paper cellulose nanocrystals were prepared by treating microcrystalline cellulose with 1-butyl-3-methylimidazolium hydrogen sulphate ionic liquid. Cellulose nanocrystals, after separation from ionic liquid, were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Field emission scanning electron microscopy (FESEM) Transmission Electron Microscope (TEM) and Thermogravimetric analysis. XRD results showed no changes in type of cellulose after the treatment with ionic liquid, however, high crystallinity index was observed in the ionic liquid treated sample. Cellulose nanocrystals, having length around 50–300 nm and diameter around 14–22 nm were observed in the ionic liquid treated sample under FESEM and TEM, and similar patterns of peaks as that of microcrystalline cellulose were observed for cellulose nanocrystals in the FTIR spectra. The thermal stability of the cellulose nanocrystals was measured low as compare to microcrystalline cellulose.     

A systems analysis tool for construction and demolition wastes management

Managing construction and demolition (C&D) wastes has challenged many municipalities with diminishing waste disposal capacity. Facing such challenges, the Massachusetts Department of Environmental Protection proposed a policy restricting the landfill disposal of certain C&D waste materials, if unprocessed. This research is to study the potential economic impact of such restriction on construction contractors and C&D waste processors. A spreadsheet-based systems analysis model has been developed to assist the cost-benefit evaluation for various C&D waste management scenarios. The model, developed based on the mass balance principle, is designed to track a C&D waste stream through the various stages of a waste management system, i.e. generation, source separation, processing, recycling, and final disposal. This model, by incorporating the material flow data with the cost/revenue data associated with each management activity, can then provide an economic analysis for a proposed C&D waste management scenario. A case study illustrating the application of this model for Massachusetts is also presented.     

Medical waste management in Ibadan, Nigeria: obstacles and prospects

Quantification and characterization of medical waste generated in healthcare facilities (HCFs) in a developing African nation has been conducted to provide insights into existing waste collection and disposal approaches, so as to provide sustainable avenues for institutional policy improvement. The study, in Ibadan city, Nigeria, entailed a representative classification of nearly 400 healthcare facilities, from 11 local government areas (LGA) of Ibadan, into tertiary, secondary, primary, and diagnostic HCFs, of which, 52 HCFs were strategically selected. Primary data sources included field measurements, waste sampling and analysis and a questionnaire, while secondary information sources included public and private records from hospitals and government ministries. Results indicate secondary HCFs generate the greatest amounts of medical waste (mean of 10,238 kg/day per facility) followed by tertiary, primary and diagnostic HCFs, respectively. Characterised waste revealed that only approximately 3% was deemed infectious and highlights opportunities for composting, reuse and recycling. Furthermore, the management practices in most facilities expose patients, staff, waste handlers and the populace to unnecessary health risks. This study proffers recommendations to include (i) a need for sustained cooperation among all key actors (government, hospitals and waste managers) in implementing a safe and reliable medical waste management strategy, not only in legislation and policy formation but also particularly in its monitoring and enforcement and (ii) an obligation for each HCF to ensure a safe and hygienic system of medical waste handling, segregation, collection, storage, transportation, treatment and disposal, with minimal risk to handlers, public health and the environment.     

Inconsistent pathways of household waste

The aim of this study was to provide policy-makers and waste management planners with information about how recycling programs affect the quantities of specific materials recycled and disposed of. Two questions were addressed: which factors influence household waste generation and pathways? and how reliable are official waste data? Household waste flows were studied in 35 Swedish municipalities, and a wide variation in the amount of waste per capita was observed. When evaluating the effect of different waste collection policies, it was found to be important to identify site-specific factors influencing waste generation. Eleven municipal variables were investigated in an attempt to explain the variation. The amount of household waste per resident was higher in populous municipalities and when net commuting was positive. Property-close collection of dry recyclables led to increased delivery of sorted metal, plastic and paper packaging. No difference was seen in the amount of separated recyclables per capita when weight-based billing for the collection of residual waste was applied, but the amount of residual waste was lower. Sixteen sources of error in official waste statistics were identified and the results of the study emphasize the importance of reliable waste generation and composition data to underpin waste management policies.     

Development of waste gasification and gas reforming system for municipal solid waste (MSW)

To achieve both high-efficiency power generation and high detoxification performance, advanced-type waste power generation plants such as pyrolysis and gas reforming plants are suggested. Further surveys on actual operational data of these plants are required in terms of reliability of the system when it is introduced to waste disposal sites. To verify the technical effectiveness of advanced-type waste power generation using the pyrolysis and gas reforming method, we evaluated 10?tons/day of municipal solid wastes (MSW) treated in a demonstration plant. A demonstration test was conducted over 100?days including 35?consecutive days of operation treating MSWs. The test results show high recycling performance and harmless nature of the plant which proves it to be an excellent waste recycling system. Major test results are as follows: (1) stabilization of waste treatment is possible with the wastes of various qualities, (2) clean gas is produced from the waste whose energy recovery ratio is approximately 40?%. (3) 99.3?% weight % of dried waste are recovered as valuable materials such as clean gas, char and metal, (4) total amount of dioxin emission to the outside of the plant is very small, down to 0.0051–0.018?μg?TEQ per ton waste.     

Life cycle assessment for optimising the level of separated collection in integrated MSW management systems

This life cycle assessment study analyses material and energy recovery within integrated municipal solid waste (MSW) management systems, and, in particular, the recovery of the source-separated materials (packaging and organic waste) and the energy recovery from the residual waste. The recovery of materials and energy are analysed together, with the final aim to evaluate possible optimum levels of source-separated collection that lead to the most favourable energetic and environmental results; this method allows identification of an optimum configuration of the MSW management system. The results show that the optimum level of source-separated collection is about 60%, when all the materials are recovered with high efficiency; it decreases to about 50%, when the 60% level is reached as a result of a very high recovery efficiency for organic fractions at the expense of the packaging materials, or when this implies an appreciable reduction of the quality of collected materials. The optimum MSW management system is thus characterized by source-separated collection levels as included in the above indicated range, with subsequent recycling of the separated materials and energy recovery of the residual waste in a large-scale incinerator operating in combined heat and power mode.     

The applicability of Fourier transform infrared (FT-IR) spectroscopy in waste management

State and stability or reactivity of waste materials are important properties that must be determined to obtain information about the future behavior and the emission potential of the materials. Different chemical and biological parameters are used to describe the stage of organic matter in waste materials. Fourier transform infrared spectroscopy provides information about the chemistry of waste materials in a general way. Several indicator bands that are referred to functional groups represent components or metabolic products. Their presence and intensity or their absence shed light on the phase of degradation or stabilization. The rapid assessment of the stage of organic matter decomposition is a very important field of application. Therefore, infrared spectroscopy is an appropriate tool for process and quality control, for the assessment of abandoned landfills and for checking of the successful landfill remediation. A wide range of applications are presented in this study for different waste materials. Progressing stages of a typical yard/kitchen waste composting process are shown. The fate of anaerobically "stabilized" leftovers in a subsequent liquid aerobic process is revealed by spectroscopic characteristics. A compost that underwent the biological stabilization process is distinguished from a "substrate" that comprises immature biogenic waste mixed with mineral compounds. Infrared spectra of freeze-dried leachate from untreated and aerated landfill material prove the effect of the aerobic treatment during 10 weeks in laboratory-scale experiments.