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Plant biomass conversion by saprotrophic fungi plays a pivotal role in terrestrial carbon (C) cycling. The general consensus is that fungi metabolize carbohydrates, while lignin is only degraded and mineralized to CO 2 . Recent research, however, demonstrated fungal conversion of 13 C-monoaromatic compounds into proteinogenic amino acids. To unambiguously prove that polymeric lignin is not merely degraded, but also metabolized, carefully isolated 13 C-labeled lignin served as substrate for Agaricus bisporus , the world's most consumed mushroom. The fungus formed a dense mycelial network, secreted lignin-active enzymes, depolymerized, and removed lignin. With a lignin carbon use efficiency of 0.14 (g/g) and fungal biomass enrichment in 13 C, we demonstrate that A. bisporus assimilated and further metabolized lignin when offered as C-source. Amino acids were high in 13 C-enrichment, while fungal-derived carbohydrates, fatty acids, and ergosterol showed traces of 13 C. These results hint at lignin conversion via aromatic ring-cleaved intermediates to central metabolites, underlining lignin's metabolic value for fungi.

Fungi are main lignin degraders and the edible white button mushroom, Agaricus bisporus, inhabits lignocellulose-rich environments. Previous research hinted at delignification when A. bisporus colonized pre-composted wheat straw-based substrate in an industrial setting, assumed to aid subsequent release of monosaccharides from (hemi-)cellulose to form fruiting bodies. Yet, structural changes and specific quantification of lignin throughout A. bisporus mycelial growth remain largely unresolved. To elucidate A. bisporus routes of delignification, at six timepoints throughout mycelial growth (15 days), substrate was collected, fractionated, and analyzed by quantitative pyrolysis-GC-MS, 2D-HSQC NMR, and SEC. Lignin decrease was highest between day 6 and day 10 and reached in total 42 % (w/w). The substantial delignification was accompanied by extensive structural changes of residual lignin, including increased syringyl to guaiacyl (S/G) ratios, accumulated oxidized moieties, and depleted intact interunit linkages. Hydroxypropiovanillone and hydroxypropiosyringone (HPV/S) subunits accumulated, which are indicative for β-|O-4' ether cleavage and imply a laccase-driven ligninolysis. We provide compelling evidence that A. bisporus is capable of extensive lignin removal, have obtained insights into mechanisms at play and susceptibilities of various substructures, thus we were contributing to understanding fungal lignin conversion., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Forensic methods to independently trace timber origin are essential to combat illegal timber trade. Tracing product origin by analysing their multi-element composition has been successfully applied in several commodities, but its potential for timber is not yet known. To evaluate this potential the drivers of wood multi-elemental composition need to be studied. Here we report on the first study relating wood multi-elemental composition of forest trees to soil chemical and physical properties. We studied the reactive soil element pools and the multi-elemental composition in sapwood and heartwood for 37 Azobé (Lophira alata) trees at two forest sites in Cameroon. A total of 46 elements were measured using ICP-MS. We also measured three potential drivers of soil and wood elemental composition: clay content, soil organic matter and pH. We tested associations between soil and wood using multiple regressions and multivariate analyses (Mantel test, db-RDA). Finally, we performed a Random Forest analysis of heartwood elemental composition to check site assignment accuracy. We found elemental compositions of soil, sapwood and heartwood to be significantly associated. Soil clay content and organic matter positively influenced individual element concentrations (for 13 and 9 elements out of 46 respectively) as well as the multi-elemental composition in wood. However, associations between wood and topsoil elemental concentrations were only significant for one element. We found close associations between element concentrations and composition in sapwood and heartwood. Lastly, the Random Forest assignment success was 97.3 %. Our findings indicate that wood elemental composition is associated with that in the topsoil and its variation is related to soil clay and organic matter content. These associations suggests that the multi-elemental composition of wood can yield chemical fingerprints obtained from sites that differ in soil properties. This finding in addition to the high assignment accuracy shows potential of multi-element analysis for tracing wood origin., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The large-scale storage and inundation of contaminated soils and sediments in deep waterlogged former sand pits or in lakes have become a fairly common practice in recent years. Decreasing water depth potentially promotes aquatic biodiversity, but it also poses a risk to water quality as was shown in a previous study on the impact on groundwater. To provide in the urgent need for practical and robust risk indicators for the storage of terrestrial soils in surface waters, the redistribution of metals and nutrients was studied in long-term mesocosm experiments. For a range of surface water turbidity (suspended matter concentrations ranging from 0 to 3000 mg/L), both chemical partitioning and toxicity of pollutants were tested for five distinctly different soils. Increasing turbidity in surface water showed only marginal response on concentrations of heavy metals, phosphorus (P) and nitrogen (N). Toxicity testing with bioluminescent bacteria, and biotic ligand modelling (BLM), indicated no or only minor risk of metals in the aerobic surface water during aerobic mixing under turbid conditions. Subsequent sedimentation of the suspended matter revealed the chemical speciation and transport of heavy metals and nutrients over the aerobic and anaerobic interface. Although negative fluxes occur for Cd and Cu, most soils show release of pollutants from sediment to surface waters. Large differences in fluxes occur for PO 4 , SO 4 , B, Cr, Fe, Li, Mn and Mo between soils. For an indicator of aerobic chemical availability, dilute nitric acid extraction (0.43 M HNO 3 ; Aqua nitrosa) performed better than the conventional Aqua regia destruction. Both the equilibrium concentrations in surface waters, and fluxes from sediment, were adequately (r 2  = 0.81) estimated by a 1 mM CaCl 2 soil extraction procedure. This study has shown that the combination of 0.43 M HNO 3 and 1 mM CaCl 2 extraction procedures can be used to adequately estimate emissions from sediment to surface waters, and assess potential water quality changes, when former sand pits are being filled with soil materials.

Knowledge on organic matter (OM) concentration and composition is of major importance for predicting Zn speciation and bioavailability in soils, especially for low-Zn soils. However, comprehensive knowledge on the effect of soil-like organic amendments such as compost on metal speciation is limited. For the first time, multisurface modeling is applied on compost to study the effect of solid and dissolved OM composition on the speciation of reactive Zn as influenced by conditions applied in frequently used extractions to estimate Zn bioavailability. First, compost OM composition was determined by fractionation in operationally defined humic, fulvic, and hydrophilic acid pools under various extraction conditions, and subsequently, Zn speciation was modeled using the generic non-ideal competitive adsorption-Donnan (NICA-Donnan) model in addition to adsorption to hydrous ferric oxide (HFO) and clay. The results show a strong effect of extraction conditions on OM concentration and composition and related dissolved Zn speciation. Model predictions show that Zn in solution is mainly bound to dissolved humic acids. Analysis of deviations between measured and modeled Zn concentrations reveal specific limitations of the current generic model parameters, particularly with regard to Zn binding to OM at low concentrations and Ca-Zn competition, that is, typical conditions that occur in low-Zn soils.

Insights into the influence of redox conditions, that is the availability of electron acceptors, and dissolved organic matter (DOM) on pesticide biodegradation in groundwater are key to understanding the environmental fate of pesticides in natural groundwater systems. Here, the influence of redox conditions and supplemental DOM addition on biodegradation of pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,6-dichlorobenzamide (BAM), mecoprop-p (MCPP) and bentazone, was tested in microcosm and subsequent column experiments. Pesticide degradation, functional genes and changes in specific fractions and quantity of DOM were systematically quantified. In aerobic microcosm experiments, the highest 2,4-D degradation rate was obtained with the presence of more assimilable DOM. In column experiments, minimal pesticide degradation (≤33.77%) in any anaerobic redox conditions was observed in the absence of DOM. However, in the presence of DOM, 2,4-D biodegradation was considerably enhanced under nitrate-reducing conditions (from 23.5 ± 10.2% to 82.3 ± 11.6%) and in a column without external electron acceptor amendment (from -6.3 ± 12.6% to 31.1 ± 36.3%). Observed preferential depletion of the fulvic acid fraction of DOM provides indications for specific functional DOM properties. The qPCR results show an increase in microbial biomass and functional genes (tfdA) in liquid phase after DOM addition. The results of this work provide insights into the interplays among DOM, redox geochemistry, and pesticide biodegradation, and show the potential of a novel approach - DOM addition to groundwater systems - for in situ biostimulation technology to remove pesticides from groundwater systems., (Copyright © 2019. Published by Elsevier B.V.)

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Natural dissolved organic matter (DOM) and nitrification can play an important role in biodegradation of pharmaceutically active compounds (PhACs) in aerobic zones of constructed wetlands (CWs). This study used an enrichment culture originating from CW sediment to study the effect of DOM and nitrification on aerobic biodegradation of seven PhACs. The enriched culture degraded caffeine (CAF), metoprolol (MET), naproxen (NAP), and ibuprofen (IBP) with a consistent biodegradability order of CAF>MET>NAP>IBP. Biodegradation of propranolol, carbamazepine, and diclofenac was insignificant (<15%). CAF biodegradation was inhibited by the easily biodegradable DOM. Conversely, DOM enhanced biodegradation of MET, NAP, and IBP, potentially by contributing more biomass capable of degrading PhACs. Nitrification enhanced biodegradation of NAP and IBP and mineralization of the PhAC mixture as well as less biodegradable DOM, which may result from co-metabolism of ammonia oxidizing bacteria or enhanced heterotrophic microbial activity under nitrification. MET biodegradation was inhibited in the presence of nitrification. DOM and nitrification effects on PhAC biodegradation in CWs gained from this study can be used in strategies to improve CW operation, namely: designing hydraulic retention times based on the biodegradability order of specific PhACs; applying DOM amendment; and introducing consistent ammonium streams to increase removal of PhACs of interest., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 CaCl 2 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., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Recently a dilute nitric acid extraction (0.43 M) was adopted by ISO (ISO-17586:2016) as standard for extraction of geochemically reactive elements in soil and soil like materials. Here we evaluate the performance of this extraction for a wide range of elements by mechanistic geochemical modeling. Model predictions indicate that the extraction recovers the reactive concentration quantitatively (>90%). However, at low ratios of element to reactive surfaces the extraction underestimates reactive Cu, Cr, As, and Mo, that is, elements with a particularly high affinity for organic matter or oxides. The 0.43 M HNO 3 together with more dilute and concentrated acid extractions were evaluated by comparing model-predicted and measured dissolved concentrations in CaCl 2 soil extracts, using the different extractions as alternative model-input. Mean errors of the predictions based on 0.43 M HNO 3 are generally within a factor three, while Mo is underestimated and Co, Ni and Zn in soils with pH > 6 are overestimated, for which possible causes are discussed. Model predictions using 0.43 M HNO 3 are superior to those using 0.1 M HNO 3 or Aqua Regia that under- and overestimate the reactive element contents, respectively. Low concentrations of oxyanions in our data set and structural underestimation of their reactive concentrations warrant further investigation.

Insight in the molecular structure of humic acid (HA) and fulvic acid (FA) can contribute to identify relationships between their molecular properties, and further our quantitative abilities to model important organic matter functions such as metal complexation and association with mineral surfaces. Pyrolysis gas chromatography/mass spectrometry (Py-GC-MS) is used to compare the molecular composition of HA and FA. A systematic comparison was obtained by using samples from different environmental sources, including solid and aqueous samples from both natural and waste sources. The chemical signature of the pyrolysates was highly variable and no significant difference between HA and FA was found for major chemical groups, that is, carbohydrates, phenols, benzenes, and lignin phenols, together accounting for 62-96% of all quantified pyrolysis products. However, factor analysis showed that within each sample, FAs consistently differed from corresponding HAs in a larger contribution from mono- and polyaromatic hydrocarbons and heterocyclic hydrocarbons, together accounting for 3.9-44.5% of the quantified pyrolysis products. This consistent difference between FAs and corresponding HAs, suggests that their binding properties may, in addition to the carboxyl and phenolic groups, be influenced by the molecular architecture. Py-GC-MS may thus contribute to identify relationships between HA and FA binding- and molecular-properties.

Alternating flooding and drainage conditions have a strong influence on redox chemistry and the solubility of trace metals in paddy soils. However, current knowledge of how the effects of water management on trace metal solubility are linked to trace metal uptake by rice plants over time is still limited. Here, a field-contaminated paddy soil was subjected to two flooding and drainage cycles in a pot experiment with two rice plant cultivars, exhibiting either high or low Cd accumulation characteristics. Flooding led to a strong vertical gradient in the redox potential (Eh). The pH and Mn, Fe, and dissolved organic carbon concentrations increased with decreasing Eh and vice versa. During flooding, trace metal solubility decreased markedly, probably due to sulfide mineral precipitation. Despite its low solubility, the Cd content in rice grains exceeded the food quality standards for both cultivars. Trace metal contents in different rice plant tissues (roots, stem, and leaves) increased at a constant rate during the first flooding and drainage cycle but decreased after reaching a maximum during the second cycle. As such, the high temporal variability in trace metal solubility was not reflected in trace metal uptake by rice plants over time. This might be due to the presence of aerobic conditions and a consequent higher trace metal solubility near the root surface, even during flooding. Trace metal solubility in the rhizosphere should be considered when linking water management to trace metal uptake by rice over time.

As part of a more circular economy, current attention on waste is shifting from landfilling towards the prevention, re-use and recycling of waste materials. Although the need for landfills is decreasing, there are many landfills around the world that are still operational or at the point of starting the aftercare period. With traditional aftercare management, these landfills require perpetual aftercare at considerable cost due to monitoring and regular maintenance of liners. In an attempt to lower these aftercare costs, and to prevent that future generations become responsible for finding a sustainable solution of present day waste, the Dutch government takes action to explore the possibilities of sustainable landfill management. A project was started to investigate whether the use of source-oriented treatment techniques (so-called active treatment) of landfills can result in a sustainable emission reduction to soil and groundwater. During the next decade, sustainable landfill management is tested at three selected pilot landfills in the Netherlands. To enable this pilot testing and to determine its success after the experimental treatment period, a new methodology and conceptual framework was developed. The aim of this paper is to describe the development of the new methodology, and in particular the policy decisions, needed to determine whether the pilot experiments will be successful. The pilot projects are considered successful when the concentrations in the leachate of the pilot landfills have sufficiently been reduced and for longer periods of time and comply with the derived site-specific Environmental Protection Criteria (EPC). In that case, aftercare can be reduced, and it can be determined whether sustainable landfill management is economically feasible for further implementation., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Colloidal phosphorus (P) may represent an important fraction of the P in natural waters, but these colloids remain poorly characterized. In this work, we demonstrate the applicability of asymmetric flow field-flow fractionation (AF4) coupled to high resolution ICP-MS for the characterization of low concentrations of P-bearing colloids. Colloids from five streams draining catchments with contrasting properties were characterized by AF4-ICP-MS and by membrane filtration. All streams contain free humic substances (2-3 nm) and Fe-bearing colloids (3-1200 nm). Two soft water streams contain primary Fe oxyhydroxide-humic nanoparticles (3-6 nm) and aggregates thereof (up to 150 nm). In contrast, three harder water streams contain larger aggregates (40-1200 nm) which consist of diverse associations between Fe oxyhydroxides, humic substances, clay minerals, and possibly ferric phosphate minerals. Despite the diversity of colloids encountered in these contrasting streams, P is in most of the samples predominantly associated with Fe-bearing colloids (mostly Fe oxyhydroxides) at molar P:Fe ratios between 0.02 and 1.5. The molar P:Fe ratio of the waters explains the partitioning of P between colloids and truly dissolved species. Waters with a high P:Fe ratio predominantly contain truly dissolved species because the Fe-rich colloids are saturated with P, whereas waters with a low P:Fe ratio mostly contain colloidal P species. Overall, AF4-ICP-MS is a suitable technique to characterize the diverse P-binding colloids in natural waters. Such colloids may increase the mobility or decrease the bioavailability of P, and they therefore need to be considered when addressing the transport and environmental effects of P in catchments., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The study aimed to understand selenium (Se) speciation and extractability in Dutch agricultural soils. Top soil samples were taken from 42 grassland fields and 41 arable land fields in the Netherlands. Total Se contents measured in aqua regia were between 0.12 and 1.97 mg kg(-1) (on average 0.58 mg kg(-1)). Organic Se after NaOCl oxidation-extraction accounted for on average 82% of total Se, whereas inorganic selenite (selenate was not measurable) measured in ammonium oxalate extraction using HPLC-ICP-MS accounted for on average 5% of total Se. The predominance of organic Se in the soils is supported by the positive correlations between total Se (aqua regia) and total soil organic matter content, and Se and organic C content in all the other extractions performed in this study. The amount of Se extracted followed the order of aqua regia > 1 M NaOCl (pH8) > 0.1 M NaOH>ammonium oxalate (pH3) > hot water>0.43 M HNO3 > 0.01 M CaCl2. None of these extractions selectively extracts only inorganic Se, and relative to other extractions 0.43 M HNO3 extraction contains the lowest fraction of organic Se, followed by ammonium oxalate extraction. In the 0.1M NaOH extraction, the hydrophobic neutral (HON) fraction of soil organic matter is richer in Se than in the hydrophilic (Hy) and humic acid (HA) fractions. The organic matter extracted in 0.01 M CaCl2 and hot water is in general richer in Se compared to the organic matter extracted in 0.1M NaOH, and other extractions (HNO3, ammonium oxalate, NaOCl, and aqua regia). Although the extractability of Se follows to a large extent the extractability of soil organic carbon, there is several time variations in the Se to organic C ratios, reflecting the changes in composition of organic matter extracted., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Dissolved organic carbon (DOC) has been proposed as an indicator of compost maturity and stability. Further fractionation of compost DOC may be useful for determining how particular composting conditions will influence DOC quality. Eleven composts ranging in input materials and processing techniques were analyzed; concentrations of DOC ranged from 428 mg kg(-1) to 7300 mg kg(-1). Compost DOC was qualified by fractionation into pools of humic acids (HA), fulvic acids (FA), hydrophobic neutrals (HoN), and hydrophilic (Hi) compounds. The range in proportion of DOC pools was highly variable, even for composts with similar total DOC concentrations. Longer composting time and higher temperatures consistently corresponded with a depletion of hydrophilics, suggesting a preferential turnover of these compounds during the thermophilic composting phase. Qualification of DOC pools through fractionation may be an informative tool in predicting the effects of a processing technique on compost quality and, ultimately, soil functional processes., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Colloids may facilitate the transport of trace elements and nutrients like phosphate in soil. In this study, we characterized soil colloids (<0.45 μm), extracted from four agricultural soils by Na-bicarbonate and Na-pyrophosphate, by two complementary analytical techniques; asymmetric flow field-flow fractionation (AF4) and X-ray absorption spectroscopy (XAS). The combined results from AF4 and XAS show that colloidal Fe is present as (i) free Fe-(hydr)oxide nanoparticles, (ii) Fe-(hydr)oxides associated with clay minerals, and (iii) Fe in clay minerals. Free Fe-(hydr)oxide nanoparticles, which can be as small as 2-5 nm, are extracted with Na-pyrophosphate but not with Na-bicarbonate, except for one soil. In contrast, Fe-(hydr)oxides associated with clay minerals are dispersed by both extractants. XAS results show that the speciation of Fe in the colloidal fractions closely resembles the speciation of Fe in the bulk soil, indicating that dispersion of colloidal Fe from the studied soils was rather unselective. In one Fe-rich soil, colloidal Fe was dominantly dispersed in the form of free Fe-(hydr)oxide nanoparticles. In the other three soils, dispersed Fe-(hydr)oxides were dominantly associated with clay minerals, suggesting that their dispersion as free nanoparticles was inhibited by strong attachment. However, in these soils, Fe-(hydr)oxides can be dispersed as oxide-clay associations and may as such facilitate the transport of trace elements.

Nearly all publications dealing with availability or bioavailability of soil pollutants start with the following statement: the determination of total pollutant content will lead to an over-estimation of risk. However, an assessment of contaminated sites should be based on the determination of mobile fractions of pollutants, and the fractions with potential for mobilisation that threaten groundwater and surface water, and the actual and potential fractions available for uptake by plants, soil microflora and soil organisms. After reviewing the literature for method proposals concerning the determination of available/bioavailable fractions of contaminants with respect to leaching, plants, microorganisms (biodegradation) and soil organisms, we propose a testing and assessment scheme for contaminated sites. The proposal includes (i) already accepted and used methods, (ii) methods which are under standardisation, and (iii) methods for which development has just started in order to promote urgently needed research., (Copyright © 2013 Elsevier B.V. All rights reserved.)

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., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Here we evaluate the performance and limitations of two frequently used model-types to predict trace element solubility in soils: regression based "partition-relations" and thermodynamically based "multisurface models", for a large set of elements. For this purpose partition-relations were derived for As, Ba, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sb, Se, V, Zn. The multi-surface model included aqueous speciation, mineral equilibria, sorption to organic matter, Fe/Al-(hydr)oxides and clay. Both approaches were evaluated by their application to independent data for a wide variety of conditions. We conclude that Freundlich-based partition-relations are robust predictors for most cations and can be used for independent soils, but within the environmental conditions of the data used for their derivation. The multisurface model is shown to be able to successfully predict solution concentrations over a wide range of conditions. Predicted trends for oxy-anions agree well for both approaches but with larger (random) deviations than for cations., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

The performance of a multisurface sorption model approach, composed of well-accepted surface complexation models in combination with published "generic" parameter sets, is evaluated for its possible use in risk assessment. For that purpose, the leaching of a broad range of potential soil contaminants (Ni, Cu, Zn, Cd, Pb, Ba, Cr, Co, Mo, V, Sn, Sb, S, As, Se) from eight diffusely and industrially contaminated soils is predicted simultaneously without any parameter optimization. The model approach includes aqueous speciation in combination with sorption to organic matter (NICA-Donnan model), Fe/Al(hydr)oxides (Generalized Two-Layer Model), and clay (Donnan model). Independent data generated by pH-static leaching experiments, performed with individual subsamples over a wide pH range (pH 0.4-12), provide a sensitive evaluation of the model performance. Root-mean-squared error values between predicted and measured log concentrations over the entire pH range, RMSE(log), are < 0.5 for Cu, Ni, Cd, Co, S, and Se, and RMSE(log) < 1 for Zn, Ba, Cr, Pb, Sn, Mo, Sn and As. The approach without parameter optimization has led to recommendations for further research with particular emphasis on identification of leaching mechanisms for Pb, Mo, Sb, and V and further expansion of the data sets to reduce the uncertainty of the available generic sorption parameters for Sn, Sb, Ba, Cr, and V.

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.

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.

We have studied the availability and leaching of polycyclic aromatic hydrocarbons (PAHs) from two contaminated materials, a tar-containing asphalt granulate (Sigma16 US-EPA PAHs 3412mg/kg) and gasworks soil (SigmaPAHs 900mg/kg), by comparing results from three typical types of leaching tests: a column, sequential batch, and two different availability tests. The sequential batch test was found to largely resemble the column test. However, the leaching of particularly the larger PAHs (>5 aromatic rings) was found to be enhanced in the batch test by up to an order of magnitude, probably due to their association with large DOC (dissolved organic carbon) molecules generated by the vigorous mixing. The release of PAHs in the two availability tests, in which the leaching is facilitated by either a high concentration of DOC or Tenax resin, was similar, although the latter test was easier to perform and yielded more repeatable results. The availability was much higher than the amount leached in the column and sequential batch tests. However, biodegradation had apparently occurred in the column test and the total amount of PAHs released by either leaching or biodegradation, 9% and 26% for asphalt granulate and gasworks soil, respectively, did equal the amount leached in the availability tests. Therefore, the availability was found to provide a relevant measure of the PAH fraction that can be released from the solid phase. These results stress the importance of using the available instead of the total amount of contaminant in the risk analysis of solid materials in utilization or disposal.

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.

In recent years, the importance of trace metal mobile fractions rather than total contents in environmental matrices is increasing in risk assessment evaluation of contaminated sites. In this study different leaching/extraction tests, aimed at the measurements of mobile fractions of trace metals and standardized at European Committee for Standardization (CEN) for the characterization of waste, have been compared with those adopted by the Italian legislation for soils. All these procedures have been applied on Venice Lagoon sediments, in order to extend the appliance of these methods to sediments and to verify the consistency of the results when different leaching tests are applied on the same sample. The results show that these tests can be applied successfully to sediments and confirm that leaching/extraction methods based on the main parameters controlling the remobilisation of trace metals are useful tools for risk-assessment, because they can allow a "transparent" interpretation in the light of key environmental variables (such as pH and DOC) controlling metal mobility. Further the use of geochemical models in support to leaching allows the assessment of trace metals mobility in the long-term.

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.

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.

This paper provides an improved understanding of the leaching behavior of waste incineration air-pollution-control (APC) residues in a long-term perspective. Leaching was investigated by a series of batch experiments reflecting leaching conditions after initial washout of highly soluble salts from residues. Leaching experiments were performed at a range of pH-values using carbonated and noncarbonated versions of two APC residues. The leaching data were evaluated by geochemical speciation modeling and discussed with respect to possible solubility control. The leaching of major elements as well as trace elements was generally found to be strongly dependent on pH. As leaching characterization was performed in the absence of high salt levels, the presented results represent long-term leaching after initial washout from a disposal site, that is, liquid-to-solid ratios above 1-2 L/kg. The leaching of Al, Ba, Ca, Cr, Pb, S, Si, V, and Zn was found influenced by solubility control from A12O3, Al(OH)3, Ba(S,Cr)04 solid solutions, BaSO4, Ca6Al2(SO4)3(OH)12 x 26H2O, CaAl2Si4O12 x 2H2O, Ca(OH)2, CaSiO3, CaSO4 x 2H2O, CaZn2(OH)6 x 2H2O, KAlSi2O6, PbCO3, PbCrO4, Pb2O3, Pb2V2O7, Pb3(VO4)2, ZnO, Zn2SiO4, and ZnSiO3. The presented dataset and modeling results form a thorough contribution to the assessment of long-term leaching behavior of APC residues under a wide range of conditions.

Carbonation of industrial alkaline residues can be used as a CO2 sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of major and trace elements, both with regard to carbonation mechanisms and the environmental properties of the (carbonated) steel slag. Carbonation was shown to reduce the leaching of alkaline earth metals (except Mg) by conversion of Ca-phases, such as portlandite, ettringite, and Ca-(Fe)-silicates into calcite, possibly containing traces of Ba and Sr. The leaching of vanadium increased substantially upon carbonation, probably due to the dissolution of a Ca-vanadate. The reactive surface area of Al- and Fe-(hydr)oxides increased with the carbonation degree, which tends to reduce the leaching of sorption-controlled trace elements. Sorption on Mn- (hydr)oxides was found to be required to adequately model the leaching of divalent cations, but was not influenced by carbonation. Consideration of these three distinct reactive surfaces and possible (surface) precipitation reactions resulted in adequate modeling predictions of oxyanion and trace metal leaching from (carbonated) steel slag. Hence, these surfaces exert a major influence on the environmental properties of both fresh and carbonated steel slag.

Mineral CO2 sequestration, i.e., carbonation of alkaline silicate Ca/Mg minerals, analogous to natural weathering processes, is a possible technology for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline Ca-rich industrial residues are presented as a possible feedstock for mineral CO2 sequestration. These materials are cheap, available near large point sources of CO2, and tend to react relatively rapidly with CO2 due to their chemical instability. Ground steel slag was carbonated in aqueous suspensions to study its reaction mechanisms. Process variables, such as particle size, temperature, carbon dioxide pressure, and reaction time, were systematically varied, and their influence on the carbonation rate was investigated. The maximum carbonation degree reached was 74% of the Ca content in 30 min at 19 bar CO2 pressure, 100 degrees C, and a particle size of <38 microm. The two most important factors determining the reaction rate are particle size (<2 mm to <38 microm) and reaction temperature (25-225 degrees C). The carbonation reaction was found to occur in two steps: (1) leaching of calcium from the steel slag particles into the solution; (2) precipitation of calcite on the surface of these particles. The first step and, more in particular, the diffusion of calcium through the solid matrix toward the surface appeared to be the rate-determining reaction step. The Ca diffusion was found to be hindered by the formation of a CaCO3-coating and a Ca-depleted silicate zone during the carbonation process. Research on further enhancement of the reaction rate, which would contribute to the development of a cost-effective CO2-sequestration process, should focus particularly on this mechanism.

This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.

In this paper, we characterize the leaching of heavy metals (Ni, Cu, Zn, Cd, and Pb) from eight contaminated soils over a wide range of pH (pH 0.4-12) using an original approach based on batch pH-static leaching experiments in combination with selective chemical extractions and geochemical modeling. The leached concentrations of the heavy metals are generally much lower than the total concentrations and show a strong pH dependency, resulting in "V-shaped" leaching curves with orders of magnitude changes in solution concentrations. The "multisurface" model used incorporates adsorption to dissolved and solid organic matter (NICA-Donnan), iron/aluminum (hydr)oxide (generalized two-layer model) and clay (Donnan model). These models were applied without modifications, and only the standard set of binding constants and parameters was used (i.e., without any fitting). The model predictions of heavy metal leaching are generally adequate and sometimes excellent. Results from speciation calculations are consistent with the well-recognized importance of organic matter as the dominant reactive solid phase in soils. The observed differences between soils with respect to element speciation in the solid phase correspond to the relative amounts of the reactive surfaces present in the soils. In the solution phase, complexes with dissolved organic matter (DOM) are predominant over most of the pH range. Free metal ions (Me2+) are generally the dominant species below pH 4. The combination of the experimental and modeling approach as used in this study is shown to be promising because it leads to a more fundamental understanding of the pH-dependent leaching processes in soils. The "multisurface" modeling approach, with the selected sorption models, is shown to be able to adequately predict the leaching of heavy metals from contaminated soils over a wide range of conditions, without any fitting of parameters.

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.

In this work we investigate to what extent we are able to predict experimental data on column leaching of heavy metals from municipal solid waste incinerator (MSWI) bottom ash, using the current knowledge on processes controlling aqueous heavy metal concentrations in combination with a multicomponent reactive transport computer model. Heavy metal concentrations were modelled with a surface complexation model for metal sorption to (hydr)oxide minerals in the bottom ash matrix. For transport modelling it was necessary to simplify the sorption modelling approach. Therefore, we determined a minimal set of components and species that still provided an adequate description of the pH dependent heavy metal behaviour. The concentration levels of the heavy metals are generally predicted to within one order of magnitude. Discrepancies between the model and the data are caused by uncertainty in modelling parameters and a still insufficient description of the dynamics of macroelement leaching and pH. In general, the simulated leaching curves show much more abrupt changes than the measurements. This observation might be an indication of non-equilibrium. Processes that have to be taken into account for further model development are the influence of non-equilibrium effects and the facilitated transport of heavy metals by dissolved organic matter.