Risk assessment of an old landfill regarding the potential of gaseous emissions--a case study based on bioindication, FT-IR spectroscopy and thermal analysis.

Risk assessment of two sections (I and II) of an old landfill (ALH) in Styria (Austria) in terms of reactivity of waste organic matter and the related potential of gaseous emissions was performed using conventional parameters and innovative tools to verify their effectiveness in practice. The ecological survey of the established vegetation at the landfill surface (plant sociological relevés) indicated no relevant emissions over a longer period of time. Statistical evaluation of conventional parameters reveals that dissolved organic carbon (DOC), respiration activity (RA(4)), loss of ignition (LOI) and total inorganic carbon (TIC) mostly influence the variability of the gas generation sum (GS(21)). According to Fourier Transform Infrared (FT-IR) spectral data and the results of the classification model the reactivity potential of the investigated sections is very low which is in accordance with the results of plant sociological relevés and biological tests. The interpretation of specific regions in the FT-IR spectra was changed and adapted to material characteristics. Contrary to mechanically-biologically treated (MBT) materials, where strong aliphatic methylene bands indicate reactivity, they are rather assigned to the C-H vibrations of plastics in old landfill materials. This assumption was confirmed by thermal analysis and the characteristic heat flow profile of plastics containing landfill samples. Therefore organic carbon contents are relatively high compared to other stable landfills as shown by a prediction model for TOC contents based on heat flow profiles and partial least squares regression (PLS-R). The stability of the landfill samples, expressed by the relation of CO(2) release and enthalpies, was compared to unreactive landfills, archeological samples, earthlike materials and hardly degradable organic matter. Due to the material composition and the aging process the landfill samples are located between hardly degradable, but easily combustible materials and thermally resistant materials with acquired stability.

Modeling the final phase of landfill gas generation from long-term observations.

For waste management, methane emissions from landfills and their effect on climate change are of serious concern. Current models for biogas generation that focus on the economic use of the landfill gas are usually based on first order chemical reactions (exponential decay), underestimating the long-term emissions of landfills. The presented study concentrated on the curve fitting and the quantification of the gas generation during the final degradation phase under optimal anaerobic conditions. For this purpose the long-term gas generation (240-1,830 days) of different mechanically biologically treated (MBT) waste materials was measured. In this study the late gas generation was modeled by a log-normal distribution curve to gather the maximum gas generation potential. According to the log-normal model the observed gas sum curve leads to higher values than commonly used exponential decay models. The prediction of the final phase of landfill gas generation by a fitting model provides a basis for CO(2) balances in waste management and some information to which extent landfills serve as carbon sink.

How to enhance humification during composting of separately collected biowaste: impact of feedstock and processing.

Conventional parameters (loss on ignition, total organic carbon, total nitrogen, C/N-ratio, respiration activity (RA4), compost status (= 'Rottegrad'), NH4-N and NO3-N) are not correlated to humification. At best, they provide information on the biological stability (status of degradation) of composts. Humic substances which are a source of stable organic matter and nutrients are discussed as a parameter describing compost quality. Thus, in the present research project a photometric method evaluating humic acids was used to characterize the quality of 211 Austrian and foreign composts made from source-separated collected biowaste or sewage sludge. Furthermore, parameters influencing the formation of humic acids during the rotting process were investigated by implementing rotting experiments in the laboratory as well as in composting plants. The analysed composts showed humic acid contents between 2.5 and 47 %, calculated on a organic dry matter (oDM) basis. In addition to the duration of treatment the main influence on humification was the feedstock used. Stabilized sewage sludge, biowaste after intensive anaerobic pre-treatment or biowaste with low reactivity (RA4) or uniform composition (e.g. mainly grass) showed a low formation of humic acids. For optimum humification the feedstock needed to contain components that are well balanced from scarcely to easily degradable compounds. Processing also influenced humification. Open windrow systems and reactor systems allow the same quality to be produced when operated well, but optimizing mineralization (e.g. very intensive aeration) showed negative effects. The positive condition required for humification is an unhurried (not too intense) degradation with long-lasting biological activity in which microbes have enough time to use the metabolic products of degradation for humification.

Evaluation of old landfills--a thermoanalytical and spectroscopic approach.

Abandoned landfills and dumps, where untreated waste materials were deposited in the past, are a main anthropogenic source of relevant gaseous emissions. The determination of stability is a crucial target in the context of landfill risk assessment. FTIR spectroscopy and simultaneous thermal analysis in association with multivariate statistical methods were applied to landfill materials in order to get information on the kind of waste and its reactivity. The spectral and thermal patterns are fingerprints of the material. Industrial waste and the material from a 5-year-old reactor landfill were distinguished from the defined classes of mechanically-biologically treated ("MBT") waste and 30 to 40-year-old stable landfills containing municipal solid waste and construction waste ("LF") by a classification model based on soft independent modeling of class analogy (SIMCA). Degradation experiments were carried out with the fresh material originating from one MBT plant that was subjected to aerobic and anaerobic conditions in lab-scale reactors. These samples were compared to samples of one reactor landfill and to the landfill fraction from the MBT plant to demonstrate the efficiency of the biological pretreatment before final disposal. Prediction models that are based on spectral or thermal characteristics and the corresponding reference analyses were calculated by means of a partial least squares regression (PLS-R). The developed models of the biological oxygen demand (BOD) and the dissolved organic carbon (DOC) were based on spectral data, the models of the total organic carbon (TOC) and total nitrogen (TN) were based on thermal data (heat flow profiles and mass spectra of combustion gases). Preliminary results are discussed. The enthalpy of the materials decreases with progressing mineralization, whereas the enthalpy of the remaining organic matter increases. The ratio of the enthalpies was used as an indicator of stability. Selected samples comprising old landfills, a recent reactor landfill, MBT landfills and MBT materials were classified according to the calculated ratios.

Determination of humic acids content in composts by means of near- and mid-infrared spectroscopy and partial least squares regression models.

Humic acids are part of the stable organic matter fraction in soils and composts. Due to their favorable properties for soils and plants, and their role in carbon sequestration, they are considered a quality criterion of composts. Time-consuming chemical extraction of humic acids and the inherent source of errors require alternative approaches for humic acids quantification. Different measurement techniques in the mid-infrared (MIR: KBr pellet technique) and near-infrared (NIR: fiber probe as well as an integrating sphere with a sample rotator) regions were applied. Partial least squares regression (PLSR) models based on infrared spectra were developed to determine humic acids contents in composts. As the wavenumber regions used (NIR: 6105-5380 cm(-1) and 4360-4220 cm(-1), MIR: 1745-1685 cm(-1) and 1610-1567 cm(-1)) represent different molecular vibrations, the importance of the methylene-group-derived vibrations for the NIR models is discussed. The correlation coefficients obtained for the KBr pellet technique, the NIR fiber probe technique, and the NIR integrating sphere (r = 0.94, 0.93, and 0.94) and the root mean square errors of cross-validation (RMSECV = 2.2% organic dry matter (ODM), 2.5% ODM, and 2.2% ODM) make the models appropriate for application in composting practice.

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.

Prediction of humic acid content and respiration activity of biogenic waste by means of Fourier transform infrared (FTIR) spectra and partial least squares regression (PLS-R) models.

Fourier transform infrared (FTIR) spectroscopy has been proven to be an appropriate analytical method for the qualitative assessment of compost stability. This study focuses on quantitative determination of two time-consuming parameters: humic acid (HA) contents and respiration activity. Reactivity/stability and humification were quantified by respiration activities (oxygen uptake) and humic acid contents. These features are also reflected by a specific infrared spectroscopic pattern. Based on this relationship partial least squares regression (PLS-R) models for the prediction of respiration activities and humic acid contents were calculated. Characteristic wavenumber regions that are assigned to the biological/chemical parameter were selected for multivariate data analysis. The coefficient of determination (R(2)) obtained for the humic acid prediction model from infrared spectra was 87% with a root mean square error of cross-validation (RMSECV) of 2.6% organic dry matter (ODM). The prediction model for respiration activity resulted in a R(2) of 94% and a RMSECV for oxygen uptake of 2.9mgg(-1) dry matter (DM).

Characterization of different decomposition stages of biowaste using FT-IR spectroscopy and pyrolysis-field ionization mass spectrometry.

The decomposition stage and stabilization of organic matter in biowaste (mixture of yard waste and kitchen waste), originating from an open windrow process, were investigated using Fourier transform infrared (FT-IR) spectroscopy and pyrolysis-field ionization mass spectrometry (Py-FIMS). These investigations provided detailed information about chemical constituents and their behavior during the composting process. The chemical compounds were classified by their molecular signals in Py-FIMS. Multivariate statistical analysis revealed, that during the composting process, the group containing lipids, fatty acids and other chemical compounds with aliphatic skeletons changed the most. Corresponding with Py-FIMS findings changes were observed in absorbance bands of infrared spectra that reflect this group of organic compounds: the aliphatic methylene bands at 2925 and 2850 cm(-1), the band of C=O vibrations of carboxylates at 1640 cm(-1) , the O-H in-plane bend of carboxylic acids, the CO2 stretch of carboxylates and the CH2 group of alkanes at around 1430 cm(-1). During decomposition these bands decreased up to a steady level that indicated stabilization. The band at 1260-1240 cm(-1) that can be assigned to the C--O stretch of carboxylic acids or to the C-N stretch of amides and the band of aromatic amines at 1320 cm(-1) disappeared completely. The nitrate band at 1384 cm(-1) appeared at a later stage of the composting process. The relative increase of chemical compounds like moieties of lignin, humic acids and tannins in the composted material contributed to the aromatic C=C band at around 1640 cm(-1).