André van Zomeren

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.

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 materials 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.

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.

Evaluation of the Single Dilute (0.43 M) Nitric Acid Extraction to Determine Geochemically Reactive Elements in Soil

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 HNO3 together with more dilute and concentrated acid extractions were evaluated by comparing model-predicted and measured dissolved concentrations in CaCl2 soil extracts, using the different extractions as alternative model-input. Mean errors of the predictions based on 0.43 M HNO3 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 HNO3 are superior to those using 0.1 M HNO3 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.

Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

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.

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.

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.

Characterisation Leaching Tests and Associated Geochemical Speciation Modelling to Assess Long Term Release Behaviour from Extractive Wastes

A pH dependent leaching test (CEN/TS 14429) and a percolation leaching test (CEN/TS 14405) developed in CEN/TC 292 have been used for the first time to characterise the release behaviour of different sulphidic mining wastes. Geochemical speciation modeling using LeachXS Orchestra provides another type of partitioning between mineral and sorptive phases than is currently practised in the mining industry. Comparing new leaching test data for seven tailings and two waste rock samples with model predictions gives new insights into release behaviour. In leaching, mineral transformations on the surface of waste rock or tailings particles, rather than bulk mineral composition, dictate release, which implies that mineralogical examinations are not necessarily relevant from a leaching perspective. Kinetic aspects of release from sulphidic waste can be addressed by testing material in different stages of oxidation or exposure to atmospheric conditions.ZusammenfassungZum ersten Mal wurde ein in der CEN/TC 292 entwickelter pH-Wert-abhängiger Auslaugungstest (CEN/TS 14429) und eine Perkolationsprüfung im Aufwärtsstrom (CEN/TS 14405) genutzt, um das Austragsverhalten verschiedener sulfidischer Bergbauabfälle zu charakterisieren. Geochemische Speziesmodellierung mit der LeachXS Orchestra Software ermöglicht eine andere Methode der Unterteilung von Mineral- und Anreicherungsphasen als die derzeit in der Bergbauindustrie praktizierten Methoden. Neue Ergebnisse der Auslaugungstests von sieben Schlämmteich- und zwei Abraumproben ermöglichen einen Vergleich mit Modellvorhersagen und erlauben neue Einblicke in das Austragungsverhalten. Beim Auslaugen wird die Lösung eher durch mineralische Transformationen auf der Oberfläche des Abraums oder der Rückstandspartikel bestimmt als durch die Gesamtgesteinszusammensetzung. Daraus lässt sich schließen, dass mineralogische Untersuchungen aus Sicht des Auslaugungsverhaltens nicht unbedingt relevant sind. Kinetische Aspekte der Austragung aus sulfidischem Abraum können berücksichtigt werden, indem das Material in verschiedenen Oxidationsstadien oder unter atmosphärischen Bedingungen getestet wird.ResumenPara caracterizar el comportamiento de liberación desde diferentes residuos de minería de sulfuros, se han usado por primera vez un test de lixiviación pH dependiente (CEN/TS 14429) y un test de lixiviación en percolación (CEN/TS 14405), desarrollados en CEN/TC 292. Un modelo de especiación geoquímica usando LeachXS Orchestra, proporciona otro tipo de particionamiento entre mineral y las fases de sorción, que es actualmente utilizado en la industria minera. La comparación entre los datos de este nuevo test de lixiviación y las predicciones del modelo, para siete colas y dos muestras de rocas residuales, muestra nuevos aspectos en el comportamiento de estos residuos. En lixiviación, las transformaciones en la superficie de la roca o de las partículas de la cola, más que la composición del seno del mineral, dictaminan la liberación, lo que implica que los exámenes mineralógicos no son necesariamente relevantes desde una perspectiva de lixiviación. Los aspectos cinéticos de la liberación desde residuos sulfurados, pueden ser realizados testeando el material en diferentes estados de oxidación o exposición a condiciones atmosféricas.抽象欧盟PH依赖溶滤试验(CEN/TS 14429)和欧盟管柱渗透浸出实验(CEN/TS 14405)首次用于描述含硫化物矿山废石的溶出特性。利用LeachXS Orchestra专家系统建立地球化学形态分析模型而提出另一种不同的矿物及吸附形态分析方法。七种尾矿和两种废石样品的溶滤试验结果与模型预测结果的对比加深了废石溶滤特征的认识。在溶滤过程中,控制滤出过程的主要因素是废石或尾矿颗粒表面的矿物质转化而不是它们的矿物质总成分,废石或尾矿的矿物学特征不一定与溶滤直接相关。测试含硫化物废石在不同的暴露、氧化阶段的物质成分可以揭示其溶出动力学性质。

Molecular Features of Humic Acids and Fulvic Acids from Contrasting Environments

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.