Biomass Pre-Extraction as a Versatile Strategy to Improve Biorefinery Feedstock Flexibility, Sugar Yields, and Lignin Purity.

Feedstock flexibility is highly advantageous for the viability of (solvent-based) biorefineries but comes with the considerable challenge of having to cope with the varying nature and typically high abundance of nonlignocellulose compounds in the most readily available residual biomass streams. Here, we demonstrate that mild aqueous acetone organosolv fractionation of various complex lignocellulosic raw materials (roadside grass, wheat straw, birch branches, almond shells, and a mixed stream thereof) is indeed negatively affected by these compounds and present a versatile strategy to mitigate this bottleneck in biorefining. A biomass pre-extraction approach has been developed to remove the detrimental extractives with (aqueous) acetone prior to fractionation. Pre-extraction removed organic extractives as well as minerals, primarily reducing acid dose requirements for fractionation and loss of hemicellulose sugars by degradation and improved the purity of the isolated lignin. We show how pre-extraction affects the effectiveness of the biorefinery process, including detailed mass balances for pretreatment, downstream processing, and product characteristics, and how it affects solvent and energy use with a first conceptual process design. The integrated biorefining approach allows for the improved compatibility of biorefineries with sustainable feedstock supply chains, enhanced biomass valorization (i.e., isolation of bioactive compounds from the extract), and more effective biomass processing with limited variation in product quality.

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis.

Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet-Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by 31 P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC.

Legal situation and current practice of waste incineration bottom ash utilisation in Europe.

Almost 500 municipal solid waste incineration plants in the EU, Norway and Switzerland generate about 17.6 Mt/a of incinerator bottom ash (IBA). IBA contains minerals and metals. Metals are mostly separated and sold to the scrap market and minerals are either disposed of in landfills or utilised in the construction sector. Since there is no uniform regulation for IBA utilisation at EU level, countries developed own rules with varying requirements for utilisation. As a result from a cooperation network between European experts an up-to-date overview of documents regulating IBA utilisation is presented. Furthermore, this work highlights the different requirements that have to be considered. Overall, 51 different parameters for the total content and 36 different parameters for the emission by leaching are defined. An analysis of the defined parameter reveals that leaching parameters are significantly more to be considered compared to total content parameters. In order to assess the leaching behaviour nine different leaching tests, including batch tests, up-flow percolation tests and one diffusion test (monolithic materials) are in place. A further discussion of leaching parameters showed that certain countries took over limit values initially defined for landfills for inert waste and adopted them for IBA utilisation. The overall utilisation rate of IBA in construction works is approximately 54 wt%. It is revealed that the rate of utilisation does not necessarily depend on how well regulated IBA utilisation is, but rather seems to be a result of political commitment for IBA recycling and economically interesting circumstances.

Assessment of biomass ash applications in soil and cement mortars.

The pH-dependent availability and leaching of major and trace elements was investigated for a wide range of biomass ash from different fuels and conversion technologies. A technical and environmental assessment of selected biomass ash for application in soil or cement mortars was performed, using both the total content and leaching of elements. A large variation in biomass ash composition, yet consistent pH dependent leaching patterns were observed for most elements and conversion technologies. Chromium showed a distinct behaviour which was hypothesized to reflect redox conditions during conversion of the biomass. The leaching based approach was found to provide a more realistic assessment of the availability of desired (i.e. nutrients) and undesired elements (i.e. contaminants) in soil systems. When applied to a reference soil at a rate of 2% by weight, the selected biomass ash increased the concentration of particularly Cr, Mo and Zn in soil solution to a level of concern. For cement applications, the release of Ba, Cr and Mo can become of concern during the second life stage, but the release was not attributed to the included biomass ash. Both soil and cement matrixes were found to control the release of elements such as Cu, V and Ni (soil) and As, Cr and Mo (cement) when compared to the released from pure biomass ash, underlining the importance of evaluating the availability and leaching of desired and undesired elements in the application scenario. Given current regulatory criteria, beneficial utilization of biomass ash in cement may be more feasible than in soil, but regulatory criteria based on leaching rather than total content of elements may widen the application potential of biomass ash.

Site-specific aftercare completion criteria for sustainable landfilling in the Netherlands: Geochemical modelling and sensitivity analysis.

A novel, regulatory accepted approach is developed that enables competent authorities to decide whether landfill aftercare can be reduced or terminated. Our previous paper (Brand et al., Waste Management 2016, 56, 255-261, https://doi.org//10.1016/j.wasman.2016.07.038) outlines the general approach, that consists of a 10-year treatment phase (e.g., aeration, leachate recirculation), in combination with site-specific Environmental Protection Criteria (EPC) for contaminant concentrations in the landfill leachate after treatment. The current paper presents the unique modelling approach by which the site-specific EPC are derived. The modelling approach is based on the use of mechanistic multi-surface geochemical models covering the main sorption processes in soils underneath the landfills, and is composed of widely-accepted surface complexation models in combination with published "generic" parameter sets. This approach enables the consideration of the main site-specific soil properties that influence the attenuation of emitted contaminants. In addition, the sensitivity of the EPC is shown for variation of the main physicochemical-assumptions and policy-based decisions. Site-specific soil properties have been found to substantially determine the EPC and include soil-pH, dissolved organic matter, and iron-(hydr)oxide content. Apart from the sorption capacity of the local soil, EPC also depend strongly on the assumed dilution with local groundwater in the saturated zone. An important policy-related decision that influences the calculated EPC is the assessment period during which the groundwater is protected. The transparent setup of the approach using geochemical modelling, the explicit consideration of site-specific properties and the achieved regulatory acceptance may also stimulate application to landfills in other countries.

When soils become sediments: Large-scale storage of soils in sandpits and lakes and the impact of reduction kinetics on heavy metals and arsenic release to groundwater.

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction. Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water.

Enhanced biodegradation at the Landgraaf bioreactor test-cell.

From 2001 to 2011, a bioreactor demonstration was performed in a 25,000m(3) (8m deep, 3500m(2) surface) test-cell. In this bioreactor, biodegradation was enhanced by premixing and homogenizing of waste, recirculation of leachate and aeration. Anaerobic biodegradation was completed within four years and was followed by two years of aeration. Ultimately a residue was obtained that had lost approximately 95% of its biogas potential. Biodegradation resulted in a significantly reduced leaching potential for dissolved organic carbon (DOC) and specific heavy metals. For other inorganic components, less progress was achieved. Increased flushing would be required for further reduction of the leaching potential. A significant reduction in chemical oxygen demand (COD) and ammonia (NH4(+)) in leachate was not demonstrated during the relative short-term aeration: COD concentrations actually increased slightly and there was no effect on NH4(+). During the project, it became clear that moisture flow through the waste followed preferential flow paths. Therefore, attention was also paid to gain better understanding of leachate flows. From a tracer test, it was concluded that part of the waste contaminants are held in immobile blocks and are to a large extent unaffected by flow occurring in the surrounding preferential flow paths.

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species.

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG-MS) analysis of the gaseous thermal decomposition products. Results of TG-MS analysis on RDF-I BA indicated that the LOI measured at 550°C was due to moisture evaporation and dehydration of Ca(OH)(2) and hydrocalumite. Results for the HW-I BA showed that LOI at 550°C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO(3) around 700°C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO(3) contents of the HW-I BA during TG-MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)(2) in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650°C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.

Characterisation of major component leaching and buffering capacity of RDF incineration and gasification bottom ash in relation to reuse or disposal scenarios.

Thermal treatment of refuse derived fuel (RDF) in waste-to-energy (WtE) plants is considered a promising solution to reduce waste volumes for disposal, while improving material and energy recovery from waste. Incineration is commonly applied for the energetic valorisation of RDF, although RDF gasification has also gained acceptance in recent years. In this study we focused on the environmental properties of bottom ash (BA) from an RDF incineration (RDF-I, operating temperature 850-1000°C) and a RDF gasification plant (RDF-G, operating temperature 1200-1400°C), by evaluating the total composition, mineralogy, buffering capacity, leaching behaviour (both at the material's own pH and as a function of pH) of both types of slag. In addition, buffering capacity results and pH-dependence leaching concentrations of major components obtained for both types of BA were analysed by geochemical modelling. Experimental results showed that the total content of major components for the two types of BA was fairly similar and possibly related to the characteristics of the RDF feedstock. However, significant differences in the contents of trace metals and salts were observed for the two BA samples as a result of the different operating conditions (i.e. temperature) adopted by the two RDF thermal treatment plants. Mineralogy analysis showed in fact that the RDF-I slag consisted of an assemblage of several crystalline phases while the RDF-G slag was mainly made up by amorphous glassy phases. The leached concentrations of major components (e.g. Ca, Si) at the natural pH of each type of slag did not reflect their total contents as a result of the partial solubility of the minerals in which these components were chemically bound. In addition, comparison of total contents with leached concentrations of minor elements (e.g. Pb, Cu) showed no obvious relationship for the two types of BA. According to the compliance leaching test results, the RDF-G BA would meet the limits of the Italian legislation for reuse and the European acceptance criteria for inert waste landfilling. RDF-I BA instead would meet the European acceptance criteria for non hazardous waste landfilling. A new geochemical modelling approach was followed in order to predict the leaching behaviour of major components and the pH buffering capacity of the two types of slags on the basis of independent mineralogical information obtained by XRD analysis and the bulk composition of the slag. It was found that the combined use of data regarding the mineralogical characterization and the buffering capacity of the slag material can provide an independent estimate of both the identity and the amount of minerals that contribute to the leaching process. This new modelling approach suggests that only a limited amount of the mineral phases that control the pH, buffering capacity and major component leaching from the solid samples is available for leaching, at least on the time scale of the applied standard leaching tests. As such, the presented approach can contribute to gain insights for the identification of the types and amounts of minerals that control the leaching properties and pH buffering capacity of solid residues such as RDF incineration and gasification bottom ash.

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure.

Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO2 pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 °C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO2 and the resulting pH reduction occurred within 24h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH±12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.

Landfill sustainability and aftercare completion criteria.

Although many countries are increasing their efforts to recycle and to re-use waste materials, landfilling will still be needed in order to dispose of wastes which cannot be recycled or treated in other ways. Since landfills will most probably be present for a long time, measures will have to be taken to reduce their (long-term) emissions. The European Commission has delegated the competent authorities to decide to end aftercare and several member states have provided regulations for this purpose. However, there is currently no guidance for long-term risk assessment to support an aftercare completion procedure for landfills. The aim of this study is to provide examples of current regulations and to demonstrate an alternative approach for a quantitative risk assessment of landfill leachate. The presented modelling approach clearly demonstrates the added value of site specific risk assessments of the long-term emissions from landfills and might provide a basis for application when the acceptance criteria for landfill will be revisited in the future. In addition, the modelling approach can be used as one of the toolboxes to perform assessments of the long-term emissions from landfill leachates and might help the competent authorities to decide whether the remaining emission potential is acceptable or not. Moreover, the results imply that local environmental conditions contribute to the acceptability of landfill emissions and are important factors in choosing a landfill location.

Proton binding properties of humic substances originating from natural and contaminated materials.

Humic substances (HS) are ubiquitous organic constituents in soil and water and can strongly adsorb metal contaminants in natural and waste environments. Therefore, understanding and modeling contaminant-HS interactions is a key issue in environmental risk assessment. Current binding models for HS, such asthe nonideal competitive adsorption (NICA)-Donnan model, are developed and calibrated against natural organic matter from soils and surface waters. The aim of this study is to analyze the proton binding properties of humic and fulvic acid samples originating from secondary materials,waste materials and natural samples in order to assess whether the charge development of these HS can be described with generic NICA-Donnan parameters. New proton binding parameters are presented for HS isolated from several natural and contaminated (waste) materials. These parameters are shown to be similar to those of HS originating from natural environments, suggesting that the NICA-Donnan model and generic binding parameters are adequate to describe proton binding to HS in both natural and contaminated materials. These findings widen the range of environments to which the NICA-Donnan model can be applied and justify its use in geochemical speciation modeling of metal mobility in contaminated (waste) materials.

Development of an automated system for isolation and purification of humic substances.

Characterization of humic substances (HS) in environmental samples generally involves labor-intensive and time-consuming isolation and purification procedures. In this paper, the development of an automated system for HS isolation and purification is described. The novelty of the developed system lies in the way the multiple liquids and columns used in the isolation/purification procedure are handled in both forward and back-elution mode by solenoid valves. The automated procedure significantly reduces the total throughput time needed, from 6-7 days to 48 h, and the amount of labor to obtain purified HS for further characterization. Chemical characterization of purified HS showed that results were in good agreement with previously published values for HS from a variety of sources, including the IHSS standard HS collection. It was also shown that the general properties of HS were consistent among the different source materials (soil, waste, aquatic) used in this study. The developed system greatly facilitates isolation and characterization of HS and reduces the risk of potential (time-dependent) alteration of HS properties in the manual procedure.

Measurement of humic and fulvic acid concentrations and dissolution properties by a rapid batch procedure.

Although humic substances (HS) strongly facilitate the transport of metals and hydrophobic organic contaminants in environmental systems, their measurement is hampered by the time-consuming nature of currently available methods for their isolation and purification. We present and apply a new rapid batch method to measure humic (HA) and fulvic (FA) acid concentrations and dissolution properties in both solid and aqueous samples. The method is compared with the conventional procedures and is shown to substantially facilitate HS concentration measurements, particularly for applications such as geochemical modeling where HS purification is not required. The new method can be performed within 1.5-4 h per sample and multiple samples can be processed simultaneously, while the conventional procedures typically require approximately 40 h for a single sample. In addition, specific dissolution properties of HS are identified and are consistent with recent views on the molecular structure of HS that emphasize molecular interactions of smaller entities over distinct macromolecular components. Because the principles of the new method are essentially the same as those of generally accepted conventional procedures, the identified HA and FA properties are of general importance for the interpretation of the environmental occurrence and behavior of HS.

Test method selection, validation against field data, and predictive modelling for impact evaluation of stabilised waste disposal.

In setting criteria for landfill classes in Annex II of the EU Landfill Directive, it proved to be impossible to derive criteria for stabilised monolithic waste due to the lack of information on release and release controlling factors in stabilised waste monofills. In this study, we present a scientific basis, which enables a realistic description of the environmental impact of stabilised waste landfills. The work in progress involves laboratory testing of different stabilisation recipes, pilot scale studies on site and evaluation of field leachate from a full-scale stabilisation landfill. We found that the pHs in run-off and in percolate water from the pilot experiment are both around neutral. The neutral pH in run-off is apparently caused by the rapid atmospheric carbonation of those alkaline constituents that are released. The soil, used as a liner protection layer, controls the release to the subsurface below the landfill. This soil layer buffers pH and binds metals. The modelling results show that the chemistry is understood rather well. Differences between predicted and actual leaching might then be attributed to discrepancies in the description of sorption processes, complexation to organic matter and/or kinetic effects in the leaching tests. We conclude that this approach resulted in a new scientific basis for environmental impact assessment of stabilised waste landfills. The integrated approach has already resulted in a number of very valuable observations, which can be used to develop a sustainable landfill for monolithic waste and to provide guidance for the management of waste to be stabilised (e.g. improved waste mix design).

Effect of accelerated aging of MSWI bottom ash on the leaching mechanisms of copper and molybdenum.

The effect of accelerated aging of Municipal Solid Waste Incinerator (MSWI) bottom ash on the leaching of Cu and Mo was studied using a "multisurface" modeling approach, based on surface complexation to iron/aluminum (hydr)oxides, mineral dissolution/precipitation, and metal complexation by humic substances. A novel experimental method allowed us to identify that the solid/liquid partitioning of fulvic acids (FA) quantitatively explains the observed beneficial effect of accelerated aging on the leaching of Cu. Our results suggestthat iron/aluminum (hydr)oxides are the major reactive surfaces that retain fulvic acid in the bottom ash matrix, of which the aluminum (hydr)oxides were found to increase after aging. A new modeling approach, based on the surface complexation of FA on iron/aluminum (hydr)oxides is developed to describe the pH-dependent leaching of FA from MSWI bottom ash. Accelerated aging results in enhanced adsorption of FA to (neoformed) iron/aluminum (hydr)oxides, leading to a significant decrease in the leaching of FA and associated Cu. Accelerated aging was also found to reduce the leaching of Mo, which is also attributed to enhanced adsorption to (neoformed) iron/aluminum (hydr)oxides. These findings provide important new insights that may help to improve accelerated aging technology.

Contribution of natural organic matter to copper leaching from municipal solid waste incinerator bottom ash.

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is a concern in many countries and may inhibit the beneficial reuse of this secondary material. The enhanced leaching of copper from three MSWI bottom ash samples by dissolved organic carbon (DOC) was investigated with specific attention for the nature of the organic ligands. A competitive ligand exchange-solvent extraction (CLE-SE) method was used to measure Cu binding to DOC. Two types of binding sites for Cu were identified and geochemical modeling showed that the organically bound fraction varied from 82% to 100% between pH 6.6 and 10.6. Model calculations showed that complexation by previously identified aliphatic and aromatic acids was unable to explain the enhanced Cu leaching from the MSWI residues. High-performance size-exclusion chromatography (HPSEC) and the standard extraction procedure to isolate and purify natural organic matter revealed that about 0.5% of DOC consists of humic acids and 14.3-25.6% consists of fulvic acids. Calculated Cu binding isotherms based on these natural organic compounds, and the nonideal competitive adsorption-Donnan (NICA-Donnan) model, provide an adequate description of the organic Cu complexation in the bottom ash leachates. The results show that fulvic acid-type components exist in MSWI bottom ash leachates and are likely responsible for the generally observed enhanced Cu leaching from these residues. These findings enable the use of geochemical speciation programs, which include models and intrinsic parameters for metal binding to natural organic matter, to predict Cu leaching from this widely produced waste material under variable environmental conditions (e.g., pH, ionic strength, and concentrations of competing metals). The identified role of fulvic acids in the leaching of Cu and possibly other heavy metals can also be used in the development of techniques to improve the environmental quality of MSWI bottom ash.