Suitability of Fly Ash for Construction and Land Applications

Doctoral Thesis

Evelina Brännvall

Department of Civil, Environmental and Natural Resources Engineering

Division of Geosciences and Environmental Engineering

Luleå University of Technology, SE-971 87 Luleå, Sweden

Acknowledgements

I cordially thank my supervisor Associated Professor Jurate Kumpiene whose patience, guidance and constructive criticism helped me to develop, improve my skills and accomplish my goal. I would like to offer my special thanks to my deputy supervisors Adjunct Professor Rolf Sjöblom and Assistant Professor Lale Andreas as well as Professor Anders Lagerkvist for supporting me during my studies, critical comments and interesting discussions which helped me to improve my work. I would like to express my very great appreciation also to:

o Colleagues at the Waste Science and Technology for the help whenever I asked and for the nice time together, especially Désirée Nordmark.

o Ulla-Britt Uvemo and Maria Gelfgren for help in the laboratory, Igor Travar and Silvia Diener for helping with ageing experiment.

o Special thanks to Nils Skoglund from Umeå University and Tommy Wikström from Luleå University of Technology for the help to pelletize the mixtures.

o All girls from Research School for Women at LTU, Elisabeth Johnsson and Rose–Marie Sundqvist for their endless support.

o My mentor Else Nordmark for her valuable advices. My warmest gratitude is for my son Tomas and my family because they are always there whenever I need them (Ačiū!). My heartfelt thanks are to my dear Daniel C. McMurry for all love, support and for help with English. The financial support provided by the EU Regional Development Fund Objective 2 project North Waste Infrastructure, the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (FORMAS), the landfill operator Telge Återvinning AB, Seth M. Kempe stipend fond and Wallenbergsstiftelsen ”Jubileumsanslaget” is greatly acknowledged.

Luleå, 2013 October

Evelina Brännvall

List of paper

This Doctoral Thesis is based on several projects, which resulted in the papers listed below and which are referred to in the text by their respective Roman numerals (Papers I-V)

Paper I Evelina Brännvall, Lale Andreas, Rolf Sjöblom, Silvia Diener and Anders Lagerkvist (2013). Factors influencing chemical and mineralogical changes in RDF fly ashes during aging. Journal of Environmental Engineering. Accepted.

Paper II Evelina Brännvall, Lale Andreas, Rolf Sjöblom and Anders Lagerkvist (2013). Changes of fly ash properties during ageing. Submitted to Waste Management.

Paper III Evelina Brännvall, Carles Belmonte Zamora, Rolf Sjöblom, Jurate Kumpiene. Effect of industrial residue combinations on availability of elements. Submitted to Waste Management.

Paper IV Evelina Brännvall, Malin Nilsson, Rolf Sjöblom, Nils Skoglund, Jurate Kumpiene. Effect of industrial residue combinations on plant uptake of elements. 2013. Journal of Environmental Management. Accepted.

Paper V Evelina Brännvall, Martin Wolter, Rolf Sjöblom, Jurate Kumpiene. Impact of pelletized fly ash and biosolids mixtures on soil environment. In manuscript.

Other papers by the author not included in the thesis:

Evelina Brännvall, Lale Andreas, Rolf Sjöblom, Silvia Diener, Anders Lagerkvist. Mineral transformations in ashes, focusing on clay minerals — A Review. In manuscript.

Sjöblom R, Ecke H & Brännvall E 2013.Vitrified forts as anthropogenic analogues for assessment of long-term stability of vitrified waste in natural environments. Int. J. Sust. Dev. & Plan. 2013. Accepted.

Kumpiene J, Desogus P, Schulenburg S, Renella G, Brännvall E, Lagerkvist A, Andreas A, Sjöblom R 2013. Utilisation of chemically stabilised arsenic-contaminated soil in a landfill top cover. Environ Sci Pollut R. DOI 10.1007/s11356-013-1818-3.

Kumpiene J, Robinson R, Brännvall E, Nordmark D, Bjurström, H, Andreas L, Lagerkvist A, Ecke H 2011. Carbon speciation in ash, residual waste 1 and contaminated soil by thermal and chemical analyses. Waste Manag 31(1) 18-25.

Kumpiene J, Brännvall E, Taraškevičius R, Aksamitauskas Č, Zinkutė R 2011. Spatial Variability of Topsoil Contamination with Trace Elements in Preschools in Vilnius, Lithuania. J Geoch Expl 108(1), 15-20.

Sjöblom R, Ecke H & Brännvall E. 2012. On the possibility of using vitrified forts as anthropogenic analogues for assessment of long-term behaviour of vitrified waste. In: Waste Management and the Environment VI. Popov, V., Itoh, H. & Brebbia, C. A. (eds.). WIT Press, p. 225-236. 12 p. (WIT Transactions on Ecology and the Environment; No. 163).

Brännvall E, Andreas L, Sjöblom R, Kumpiene J. & Lagerkvist A. 2011. Ageing of ashes in a landfill top cover. In: SARDINIA 2011: Thirteenth International Waste Management and Landfill Symposium, S. Margherita di Pula, Cagliari, Italy; 3 - 7 October 2011. Cossu, R. (ed.). Cagliari: CISA Publisher, Italy, 9 p.

Diener S, Brännvall E & Andreas L. 2010. Leaching properties of steel slags after ageing under laboratory and field conditions. In: Third International Conference on Accelerated Carbonation for Environmental and Materials Engineering: ACEME10 November 29 - December 1, 2010, Åbo Akademi University, Åbo/Turku, Finland: proceedings. Zevenhoven., R. (ed.). Åbo: Åbo Akademi, 6 p.

Brännvall E, Andreas L, Diener S, Tham G, Sjöblom R. & Lagerkvist A. 2010. Formation of secondary mineral phases during the ageing of RDF fly ashes. The 6th Intercontinental Landfill Research Symposium. Japan, p. 110-112.

Diener S, Andreas L, Brännvall E & Lagerkvist A 2010. Evaluation and discussion of steel slag mineralogy after ageing under laboratory and field conditions. The 6th Intercontinental Landfill research Symposium. Japan, p. 107-109.

Brännvall E, Andreas L, Diener S, Tham G, Lagerkvist A 2009. Influence of accelerated ageing on acid neutralization capacity and mineralogical transformations in Refuse-derived-fuel fly ashes. Twelth International Waste Management and Landfill Symposium, S. Margherita di Pula, Cagliari, Italy; 5 - 9 October 2009. Cossu, R. (ed.). Cagliari: CISA Publisher, Italy, p. 524-532.

Summary

Increase of energy recovery from municipal solid waste by incineration results in the increased amounts of fly ash that has to be taken care of. Material properties should define whether fly ash is a waste or a viable resource to be used for various applications. Suitability of fly ash either as a liner material or as amendment for soil in vegetation layer in a landfill top cover was evaluated.

Three types of fly ashes have been investigated in the laboratory experiments. Namely municipal solid waste incineration (MSWI), refuse-derived-fuel (RDF) and biofuel fly ashes. Factors influencing changes in chemical properties and mineralogical composition of RDF fly ash exposed to environmental conditions close to those likely to be found in a landfill top cover were evaluated in the accelerated ageing experiment. Element availability to leaching and plant uptake in soil amended with MSWI, biofuel fly ashes and biosolids was also evaluated.

RDF fly ash exposed to the conditions corresponding to those likely to occur in a landfill top cover (20% CO2, 65% RH, 30°C T) lead to the chemical and mineralogical transformations that resulted in reduced leaching of most of the elements studied here. Only concentrations of chlorides in the leachates were an issue, because they still exceeded the leaching limit values; nevertheless the leaching of this element in aged ash decreased by 50% compared to fresh ash.

Application of pelletized MSWI fly ash with biosolids on soil resulted in elevated total concentrations of arsenic, cadmium and lead in soil (by 29%, 100% and 300%), but dissolved concentrations of these elements in soil pore water, except the arsenic, were low as in the range of drinking water concentrations (98/83/EC). Furthermore, the concentrations of cadmium and lead in plant biomass were negligible regardless of the type of ash used.

Element availability for plants showed that application of both MSWI and biofuel fly ashes do not increase element accumulation in plants. Therefore, total concentrations of elements in fly ash do not directly reflect their behaviour and potential impacts on soil and plants. Responsible application of MSWI ashes is, however, warranted in order to avoid element accumulation in soil and elevation of background values over time.

Based on the observations, RDF fly ash is considered as a suitable material to be used in a landfill liner. Whereas MSWI and biofuel fly ashes based on element availability for plants studies, could be considered suitable for land applications.

Abbreviations

ANC Acid neutralization capacity

ANC 8.3 Amount of acid necessary to titrate from the samples natural pH down to pH 8.3

ANC 4.5 Amount of acid necessary to titrate from pH 8.3 down to pH 4.5

BA Bottom ash

BFA Biofuel fly ash

CEC Cation exchange capacity

CV Coefficient of variation

dw Dry weight

EDX Energy-dispersive X-ray spectroscopy (also EDS)

FA Fly ash

ICP-AES Inductively coupled plasma atomic emission spectroscopy

ICP-MS Inductively coupled plasma mass spectrometry

ICP-SFMS Inductively coupled plasma sector field mass spectrometry

L/S ratio liquid to solid ratio

MFA MSWI fly ash

MSW Municipal solid waste

MSWI Municipal solid waste incineration

Mt Million tones

n Number of samples

MVDA Multivariate data analysis

PCA Principal Component analysis

PLS Partial Least Square projections to latent structures

RDF Refuse-derived-fuel

STDVE Standard deviation

SEM Scanning electron microscopy

TS Total solids

XRD X-ray diffraction

TABLE OF CONTENT

1. Introduction and Background ......................................................................... 1 1.1 Properties of fly ashes .......................................................................................................... 1 1.2 Application of fly ash in a landfill top cover ........................................................................ 5

2. The Scope of the Thesis ................................................................................. 8 3. Materials and Methods ................................................................................... 8

3.1 Materials .............................................................................................................................. 8 3.1.1 Fly ash .......................................................................................................................... 8 3.1.2 Other materials and substrates ...................................................................................... 9

3.2 Ageing of fly ash.................................................................................................................. 9 3.3 Material mixtures .............................................................................................................. 10 3.4 Soil fertilization ................................................................................................................. 11

3.4.1 Powdered materials .................................................................................................... 11 3.4.2 Pelletized materials ..................................................................................................... 11 3.4.3 Plant biomass and element uptake .............................................................................. 11 3.4.4 Soil pore water ........................................................................................................... 11

3.5 Evaluation Methods .......................................................................................................... 12 3.5.1 Analytical methods ..................................................................................................... 12 3.5.2 Element extractions .................................................................................................... 12 3.5.3 Acid neutralisation capacity ........................................................................................ 12 3.5.4 Leaching potential calculation .................................................................................... 12 3.5.5 Mineralogical composition ......................................................................................... 13 3.5.6 Geochemical modelling ............................................................................................. 13 3.5.7 Multivariate Data Analysis .......................................................................................... 13 3.5.8 Model evaluation ....................................................................................................... 13

4. Discussion ................................................................................................... 13 4.1 Ageing of fly ash under various environmental conditions ............................................... 13

4.1.1 Mineralogical transformations in aged ashes ............................................................... 13 4.1.2 Element solubility in aged ashes ................................................................................. 15

4.2 Element availability in fly ashes used as soil fertilizers ....................................................... 16 5. Conclusions ................................................................................................ 21 6. Outlook ...................................................................................................... 21 7. References .................................................................................................. 22

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Evelina Brännvall, Waste Science & Technology, LTU 2013

1. Introduction and Background

Sweden’s goal is to generate 100% of its energy from renewable resources (Gustavsson et al., 2011). During the last 5 years, energy recovery from renewable resources such as municipal solid waste (MSW) has increased by 8%. Almost 52% of all MSW being recycled is used for energy recovery by incineration (Avfall Sverige, 2008). Such increase can be attributed to the landfill ban of sorted combustible waste in 2002 and organic waste in 2005. This incineration reduces MSW volume by 90% and its weight by 75%. However, the remaining incineration residues (ashes) still have to be dealt with. According to EU Directive 2000/76/EC on the incineration of waste, the amounts and harmfulness of these residues must be minimised and the residues should be recycled where appropriate.

During combustion processes bottom and fly ashes are generated. Bottom ash (BA) is a non-combustible residue that remains in the incinerator, and fly ash (FA) comprises the fine particles that rise with the flue gases during combustion. In 2012, 0.85 Mt of bottom ash and ca 0.26 Mt of fly ash were generated from waste incineration in Sweden (Avfall Sverige, 2012). Bottom ash is used in various applications, but fly ash is often landfilled or sent abroad for stabilization because it is considered a hazardous waste (Sjöblom, 2013). These approaches to fly ash are both costly, and highlight the need for alternative and sustainable management solutions.

Large amounts of materials are needed in construction and land cultivation sectors. In Sweden alone about 87 Mt of natural material is required to cover ca 15-20 km2 of landfills according to the data from 2008 (Hansson, 2008). In addition, the global demand for fertilizer nutrients (currently from natural resources) is rapidly increasing and it is estimated to increase up to 2% per year until 2015 (FAO, 2011). Therefore both ash recycling and preservation of natural resources can be solved by using fly ashes as a secondary construction material and as soil fertilizer.

However, not all fly ashes are suitable for recycling. For example, most ashes cannot be applied on the forest soil because of the presence of hazardous compounds. But those ashes that are not suitable for such application can still be used e.g. in a vegetation layer of a landfill top cover. Here standard environmental monitoring systems such as leachate collection/treatment are installed, minimizing the risk for spreading of the hazardous compounds into the surrounding environment.

Fly ash could also surpass other materials (e.g. clays) commonly used in landfill top cover liners for strength and endurance in construction, as shown in recent years (Lindberg and Price, 1999, Ashmawy, 2003, Mácsik et al., 2006, Tham and Andreas, 2008 and Travar et al., 2009). Therefore material properties should define whether fly ash is a waste or a viable resource to be used for various applications.

1.1 Properties of fly ashes

MSW is very heterogeneous, consisting of diverse unburned organic and inorganic materials. These wastes can either be mass burnt directly as received without pre-treatment, or sorted, separated and reduced in size prior to incineration. This separation results in a more homogeneous material called refuse-derived-fuel (RDF),

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which consists of wastes such as tainted wood (31–73 %), recycled fuels (~30 %); peat (~23 %); plastics (~22 %); various oils (9 %) and other materials (5.3–8 %) (Nagano et al., 2000; Söderenergi, 2009). Wood (biofuel) fly ash, in contrast, originates from combustion of purely wood-based fuels.

The chemical composition of MSW may vary from source to source and also within the same incineration facility. Municipal solid waste incineration (MSWI) ashes are products of incineration at 850°C. This promotes the formation of amorphous glass phases (>40 %), which play a key role in fly ash reactivity (Bayuseno, 2006; Haiying et al., 2007). The most abundant constituents of MSWI fly ash are oxides of Ca, Si, Al, Na and Fe, which frequently occur as mixed oxides (Figure 1). MSWI and RDF fly ash also contain significant amounts of chlorine, originating from the various types of plastics like PVC (polyvinyl chloride) in the waste, and paper waste from bleaching processes (Pichtel, 2005; Pettersson et al., 2008). Also, heavy metals like Cr, Cd, Cu, Ni, Pb, Zn and etc., are accumulated in fly ashes.

Figure 1. Ternary diagram showing relative proportions of SiO2, Al2O3 and CaO, K2O, Na2O, MgO and Fe2O3 in various fly (FA) and bottom (BA) ashes according to the following references: Baciocchi et al., 2010; Bedia, 2005; Chang et al., 1997; Chang et al., 1999; Chang et al., 2006; Conn et al., 1999; Evangelou, 1996; Fernandez Bertos et al., 2004; Haiying et al., 2007; Herbert, 1996; Levandowski and Kalkreuth, 2009; Liu et al., 2004; Nogami et al., 2001; Pan et al., 2008; Polettini and Pomi, 2004; Polettini et al., 2004; Polettini et al., 2009; Rendek et al. 2006; Shi et al., 2009; Taylor and Lichte, 1980; Todorovic et al., 2003; Vassilev and Vassileva, 2009; Yan et al., 2008; Yeheyis et al., 2009, Yoshiie et al., 2002.

The chemical composition of biofuel fly ash is difficult to generalize. Its properties not only depend on plant species and which parts are combusted, but also on the types of fuels that are co-combusted with wood, as well as the collection and storage conditions of that wood prior to combustion (Demeyer et al., 2001). Biofuel fly ash usually contains high concentrations of Si, Al, Fe, Ca, S, Mg, P, K, Na and Mn (Vassilev et al., 2010 and 2012).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Mineralogical composition of MSWI as well as RDF fly ashes consists of mixtures of silicates, oxides, carbonates, sulphates and chlorides, while biofuel fly ash contains less chlorides, but more phosphates (Table 1).

Table 1. Mineralogical composition of RDF, MSWI and biofuel fly ashes.

Group/ Mineral name Formula RDF MSWI Biofuel (wood)

Fresh Aged 1 2 3 4 5

CARBONATES

Calcite CaCO3 17; 3 1; 11; 13; 25; 2;11;12 16; 18; 21; 15

Fairchidite K2Ca(CO3)2 21; 25 Huntite Mg3Ca(CO3)4 15

Magnezite MgCO3 13 Natrite Na2CO3 8

Vaterite CaCO3 3 12

CLAY MINERALS Illite KAl3Si3O10 (OH)2 1

Syngenite K2Ca(SO4)2H2O 22 2 16

CHLORIDES Blixite Pb2Cl-x(O,OH)2x 26

Cotunnite PbCl2 26

Halite NaCl 17; 4; 3 1; 5; 8; 9; 11-14; 19; 25; 2; 11; 12

Hydrocalumite

Ca8Al4 (OH)24 (CO3 )(Cl)

3; 4 1; 12;

Hydrophilite CaCl2 6

Sylvite KCl 4; 3 14 18; 21 Zinc Chloride ZnCl2 1

HYDROXIDES Boehmite ALOOH 2

Lepidocrocite FeOOH 1 Nordstrandite Al(OH)3 12

Portlandite Ca(OH)2 4; 4 2; 8; 11; 12 16; 21

OXIDES Calcium aluminum oxide Ca3Al2O6 15

Calcium titanite CaTiO3 1 Corundum Al2O3 12

Grossite CaAl4O7 5 Hematite Fe2O3 7 1; 13; 2

Lime CaO 12; 25 21 Magnetite Fe3O4 1

Minium Pb3O4 1 Periclase MgO 7 21

Rutile TiO2 1; 2 Ulvöspinel Fe2TiO4 1; 2

PHOSPHATES Aluminum phosphate AlPO4 15

Hydroxiapatite Ca5(PO4)3(OH) 21

SILICATES Akermanite Ca2Mg(Si2O7)

Albite NaAlSi3O8 16; 15 Amorphous glass 1 16

Anorthite CaAl2Si2O8 5 Augite Ca3Na3Mg3FeAl1.6 Si7O24 1

Calcium silicate hydrate Ca1.5SiO3.5·xH2O 7 11 Cristobalite SiO2 2

Diopside CaMgSi2O6 1

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1 2 3 4 5 Enstatite (Mg,Fe)SiO3 1 Feldspar 25

Ferrosilicate, magnesian (Fe,Mg)SiO3 15

Forsterite (Mg,Fe)2SiO4 1

Garnet Ca3(Al,Fe)2(Si,P)3O12 1 Gehlenite Ca2Al2SO7 3 1; 11; 12; 25; 2; 12; 13 15

Gismondite CaAl2Si2O8 · 4H2O 8 Hatrurite Ca3SiO5 1 Kalsilite KAlSiO4 1

Kilchoanite Ca3Si2O7 10 Larnite Ca2SiO4 1; 9

Merwinite Ca3Mg(SiO4)2 21 Microcline K2AlSi3O8 16

Mullite Al2O3·SiO2 16 Nepheline Na3 KAl4Si4O16 1 Plagioclase (Na,Ca)((Si,Al)AlSi2O8) 21

Quartz SiO2 6; 4; 24; 3 1; 11-13; 19; 25; 2; 8; 11; 12

16; 18; 21; 15

Sanidine KAlSi3O8 1; 5 21 Sodalite Na4Al3Si3O12Cl 1

Tobermorite Ca5(OH)2SiO16 ·4H2O 1

SULPHATES Allenite MgSO4·5H2O 5 Alunite KAl3 (SO4)2 (OH)6 1

Anhydrite CaSO4 6; 17; 7; 3 1; 8; 11-14; 19; 23; 25 2 11 12

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Aphthitialite K3Na(SO4)2 15

Bassanite CaSO4·0.5H2O 1; 2 Caracolite Na3 Pb2(SO4)3Cl 1; 2 Ettringite 3CaO·Al2O3·3CaSO4·32H2O 4; 3 1; 20 15 Gordaite NaZn4(SO4)(OH)6 Cl(H2O)6 1; 2 Gypsum CaSO4·2H2O 17 1; 11

SULPHIDES Marcasite FeS2 1

Pyrite FeS2 1 1Bayuseno et al., 2009; 2Bayuseno, 2006; 3Brännvall et al., 2009; 4Brännvall et al. 2011; 5Chandler et al., 1997; 6Conn et al., 1999; 7Dahl et al., 2009; 8Ecke et al., 2002; 9Ecke et al., 2003; 10Haiying et al., 2007; 11Jiang et al., 2009; 12Li et al., 2007; 13Lima et al., 2008; 14Mangialardi et al., 1999; 15Mellbo et al., 2008; 16Naik et al., 2002; 17Pierre et al., 2000; 18Serafimova et al., 2011; 19Shi and Kan, 2009; 20Shimaoka et al 2002; 21Steenari and Lindqvist, 1997; 22Steenari et al 1999.; 23Ubbriaco et., 2001; 24Vassilev et al., 1999;.25Wilewska-Bien et al., 2007; 26Yvon et al., 2006.

Fly ash properties depend on the environmental conditions they are exposed to. Whether they are simply landfilled, used as construction materials or applied on soil, ashes are subject to transformations, occurring when they are not in thermodynamic equilibrium with atmospheric or other conditions. Temperature and humidity fluctuations, atmospheric gases or acid rain are key factors influencing these changes. Complex chemical and mineralogical transformations occurring in fly ash include hydrolysis/hydration of Al, Ca, K and Na oxides, dissolution/precipitation of salts and hydroxides, carbonation, neo-formation of clay-like minerals, oxidation/reduction, and formation of solid solutions (Costa et al., 2007; Ecke et al., 2003; Meima et al., 2002; Ubbriaco et al., 2001; Zevenbergen et al., 1996) (Table 2).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Table 2. Mineral changes that occur during ageing of fly ash (adapted from Donahoa, 2004).

Process Mineral changes Chemical reaction Hydration Anhydrite to gypsum: CaSO4+2H2O→CaSO4·2H2O Ettringite formation 3CaSO4+Ca3Al2O6+32H2O→Ca6Al2(SO4)3(OH)

12· 26H2O Lime to portlandite: 2CaO+H2O→2Ca(OH)2 Solution/ Dissolution

Dissolution of gypsum: CaSO4→Ca2++SO42-

Hydrolysis Dissolution of glass: (schematic reaction)

Me-Al-Si-O glass+H2O+H+→Me++Al(OH)3(am)+SiO2(am)

Carbonation Portlandite to calcite: Ca(OH)2+CO2→CaCO3+H2O Ettringite to calcite and

gypsum Ca6Al2(SO4)3(OH)12·26H2O + 3CO2 → 3CaCO3+3(CaSO4·2H2O)+Al2O3 H2O+25H2O

Oxidation Magnetite to hematite: 2Fe3O4+0.5O2→3Fe2O3 Precipitation Ferric hydroxide: Fe3++3OH-→Fe(OH)3

Ettringite 3CaSO4+Ca3Al2O6+32H2O→Ca6Al2(SO4)3(OH)12· 26H2O

Adsorption Heavy metals on oxides: Fe-OH+Me2+→Fe-OMe++H+ Co-precipitation

Ideal solid solution between Fe(OH)3 and Me(OH)2:

Fe(OH)3(s)+Me2+→Me(OH)2(s)+Fe3++OH-

Note: Me - metal cation; am - amorphous

Ageing of fly ash causes pH to change, which in turn strongly influences mobility of potentially hazardous compounds in it. Formation of certain solid phases, such as clay minerals, are of main interest because of their high cation exchange capacity (3–150 cmol kg-1), which increases retention of trace elements (Mitchell and Soga, 2005; Meunier, 2005). The key factor in clay-like mineral formation is the high pH of ashes. The high pH promotes the prompt dissolution of certain compounds of aluminosilicate glass phase, which is a prerequisite for the formation of clay minerals over time (Zevenbergen et al., 1999).

Fly ash used in a landfill top cover will be subject to ageing and mineral transformation processes that are similar to those observed in previous studies of other ashes exposed to other conditions (Zevenbergen et al. 1996; 1998 and 1999; Warren and Dudas, 1985). It might be expected that in the long-term, fly ashes could possibly transform into clay-like materials with similar advantageous chemical and geotechnical properties that are beneficial for the stability of the landfill top cover.

1.2 Application of fly ash in a landfill top cover

Design. A landfill top cover is a multilayer construction that protects the environment from gas emissions from the landfill body and hinders water infiltration into the waste (Figure 2). According to Swedish and EU legislation, the amount of percolating water must not exceed 50 l (m2 yr)−1 for non-hazardous waste landfills and 5 l (m2 yr)−1 for hazardous waste landfills (SFS, 2001). The protection layer protects the liner from freezing/thawing, desiccation, root penetration and digging animals, while the upper drainage layer protects it from water percolating from above and the bottom drainage layer provides protection from gas penetrating from the waste body below the liner.

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Figure 2. Illustration of a landfill top cover system (design according to Tham and Andreas, 2008).

Prevailing conditions. The atmosphere below the liner contains water-saturated landfill gas, and the atmosphere above the liner may be affected by the run-off water from the layers above it. However the protection layer and vegetation on it retains the largest part of the moisture and only ca. 25 % of precipitated water will reach the drainage layer above the liner (Andreas et al., 2005). Humidity is an important factor for hydration and carbonation reactions to occur, which in turn affect mineralogical changes in the fly ash used as a liner material. Maximal and rapid carbonation occurs at 50 to 70% humidity (Bertolini, 2004; Sullivan-Green et al., 2007), while on either side of this range the carbonation rate decreases (Walton et al., 1997; Fattuhi, 1988). At 100% humidity, carbon dioxide penetrates material very little due to the low diffusion rate of CO2 in water.

The gas below the liner consists primarily of CH4, N2, CO2 and O2. The typical concentration (by volume) of carbon dioxide in landfill gas is between 20 and 50% (Lagerkvist, 2003). The absorption of CO2 by alkaline material leads to carbonation reactions, which in turn promote the pH decrease and affect leaching behaviour of various compounds in the liner material.

The temperature in and around the liner is influenced by the heat generated and released from the waste below; the heat conductivity of the cover layers; and the climatic conditions of the location. As the rate of waste decomposition gradually decreases, heat production declines and, hence, the temperature below the liner falls over time. Heat generation from the landfill body can lead to evaporation and subsequent desiccation in both above and below the liner. Desiccation can cause crack formation in the liner, thereby allowing water to migrate into the waste and generate leachate (Dwyer, 2000). Temperatures between +15°C and +40°C below the liner (at about 3 m depth) and between -1°C to +47°C above the liner (at about 2 m depth) have been recorded (Tham and Andreas, 2008). The high temperatures in

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Evelina Brännvall, Waste Science & Technology, LTU 2013

the protection layer above the liner were probably caused by methane oxidation. Hydration and carbonation are also heat generating or exothermic reactions (Fernandez Bertos et al., 2004). The generated heat enhances the short-term reactivity of material, and that affects changes within mineral phases (Hassett and Eylands, 1997). At temperatures up to 60°C carbonation of material increases, but at higher temperatures carbonation decreases due to decrease of water content (Liu et al., 2001; Soroka, 1993). The most beneficial temperature range for carbonation is from 20 to 30°C (Sullivan-Green et al., 2007; Soroka, 1993).

Fly ash in a vegetation layer. Several studies showed that fly ash can be used as a nutrient source to promote vegetation growth or to stabilize the contaminated soil used in a protection/vegetation layer (Figure 2) (Kumpiene et al., 2007, 2009). The main function of the vegetation layer of the landfill top cover is to sustain plant growth so that the landfill surface is protected against erosion. Plants help to minimise the amount of percolating water through evapotranspiration and nutrient-rich substrates are therefore desirable to ensure a high biomass development. Fly ash, as a source of P, Ca, Mg and K, makes it attractive as soil fertiliser. However, it lacks sufficient amounts of N.

Nitrogen is often the limiting nutrient for the biomass growth, therefore considering ashes as fertilisers, additional N source is needed, e.g. in the form of biosolids. Application of biosolids on soil increases the content of organic matter, improves the water-holding capacity of soil, and most importantly, supplies N and P. Thus, by combining ash with biosolids, a better balance between the macronutrients (N, P, K) in the material mixtures can be achieved. At the same time, such mixing may lead to chemical reactions which can be expected to reduce leaching of potentially toxic elements (e.g. Cd and Pb) in ash and biosolids by immobilizing them within the mixture matrix.

Due to the very high alkalinity of fresh ash (pH≈12), a direct application to soil is not recommended. Ashes must mature before application onto soil, in order to avoid disturbance of the nitrogen balance there (Ribbing, 2007). For this reason granulation/pelletizing are frequently used in order to transform the raw ash into a product that has a lower pH and is easier to handle. Granulated materials have a smaller surface area compared to powdered ones leading to a reduced reactivity and a slower release of ash constituents (e.g. Eriksson, 1998; Larsson & Westling, 1998; Steenari et al., 1998, Nieminen et al., 2005). This in turn, might increase the possibility for plants to take up nutrients over a more extended period of time.

Today MSWI fly ashes are classified as a hazardous waste due to the leaching of chemical elements from them, however ageing may transform fly ash into material having different properties compared to fresh ash. Based on the background described above it can be concluded that much of the internal and external factors influencing element availability in the fly ashes have yet to be understood. These knowledge gaps and several important questions have been identified: will a landfill top cover liner containing fly ashes remain chemically stable for a long time? How will fluctuating environmental conditions found in a landfill top cover change fly ash properties? Can element availability in MSWI fly ash be similar to that of biofuel fly ash? Can nutrient availability in fly ashes be matched to those of commercial fertilizers and if so, then how?

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2. The Scope of the Thesis

The aim of this study lies in evaluation of the suitability of fly ash for a landfill top cover either (1) as a liner material or (2) as amendment for soil in vegetation layer.

The following questions cover the focus of the thesis:

• How are the chemical properties and mineralogical composition of fly ash changing during ageing under environmental conditions close to those that are found in a landfill top cover?

• How does element availability change when fly ashes are combined with other materials?

• What impact do fly ash and material combinations have on element distribution in soil?

3. Materials and Methods Many of the methods used are standardized and well established and are described in detail in the respective papers. Only the key methods and their peculiarities are outlined in this section.

3.1 Materials

3.1.1 Fly ash

Refuse-derived-fuel (RDF) fly ash. The RDF fly ash (Figure 3) used in the experiment originated from incineration of sorted industrial, household, construction and demolition wastes, as well as cellulose industry by-products to generate heat and electricity. The fly ash consisted of a mixture of the ash captured in the electrostatic and bag filters in the incinerators and also the residue from semi-dry lime injection processes (Papers I-II).

Figure 3. Refuse-derived-fuel fly ash.

Biofuel fly ash (BFA). Fresh and dry (without added water) BFA from combustion of tree bark was collected from a fluidized bed incinerator (Figure 4) (Papers III-V).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Figure 4. Industrial residues and materials. BFA – biofuel fly ash, MFA- MSWI fly ash, BioS – biosolids, P – peat, Pr – peat residues, Gbw – gypsum board waste.

Municipal solid waste incineration fly ash (MFA). Fly ash from a municipal solid waste incineration (MSWI) was collected from a storage pile in a landfill (Figure 4). The sampling of this ash was done during the two separate occasions. The ash (MFAG) samples during the first occasion was used for the preparation of granules (MFA1-MFA3) and ash (MFAP) sampled later was used for the preparation of pellets (MFA4). The fuel comprised household waste, animal by-products, recycled wood chips, sleepers containing creosote and certain other hazardous wastes (Papers III-V).

3.1.2 Other materials and substrates

Other materials. Dewatered, anaerobically digested biosolids (BioS) were collected from the storage pile at a sewage water treatment plant (Figure 4) (Papers III-V). Commercially available peat (P) and gypsum boards (Gbw) were obtained from a local retailer. Peat residue (Pr), a fine fraction remaining after production of a sorbent for clean-up applications, was obtained from a company (Figure 4) (Papers III and V). Synthetic phosphate compounds, CaK2P2O7 and CaKPO4, were prepared at Umeå University, Sweden (Sandström and Boström, 2008), and were used for comparison reasons.

Substrates. Forest soil collected in two separate occasions in Luleå, Sweden, was air dried, homogenized and sieved to a <4 mm fraction. Soil (Soil) was used for the soil fertilization experiment with powdered materials and soil (Soil4) was used for the soil fertilization experiment with pelletized materials (Papers IV-V).

3.2 Ageing of fly ash The experiment was performed applying a reduced D-optimal factorial design, created with MODDE 8.0 software package (Eriksson, 2008), in which the following factors were varied at two, three or four levels and at two intermediate points: carbon dioxide (CO2 %), temperature (ºC), relative air humidity (RH %), ageing time (months) and the quality of added water (distilled or leachate from previous experiments described in Tham and Andreas, 2008) (Table 3) (Papers I-II).

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Table 3. Ageing factors and their applied levels in the reduced D-optimal factorial design for the accelerated refuse-derived-fuel fly ash ageing experiment.

Factor Low Intermediate High Carbon dioxide, CO2 (%) Atmospheric (0.038) 20* 100 Temperature, ºC 5 30 60 Relative air humidity, RH (%) 30 65 100 Time, months 3 10, 22 31 Water quality Distilled – Leachate

* Mixture of 20% CO2 and 80% N2

The influence of these factors on the chemical stability in terms of pH, acid neutralisation capacity (ANC) and leaching behavior of RDF ashes was investigated. The detailed description (Figure 5) and explanation of the experiment can be found in Papers I and II.

Figure 5. Experimental set up for the long-term laboratory experiment of fly ash ageing.

3.3 Material mixtures

Materials were combined in various proportions (Figure 1 in Paper III). Biofuel fly ash was mixed with peat and biosolids (BFA1), biofuel fly ash mixed with peat residues and biosolids (BFA2), biofuel fly ash mixed with gypsum board and biosolids (BFA3) and biofuel ash mixed with biosolids (BFA4) (Figure 6). Also, the mixtures were prepared using MSWI fly ash in the same manner as biofuel fly ash and were named as follows: MFA1, MFA2, MFA3 and MFA4 (Figure 6).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Figure 6. Granulated and pelletized fly ash and other material mixtures. For abbreviations see chapter 3.3.

3.4 Soil fertilization

3.4.1 Powdered materials

One kg of each of the final mixtures was placed in plastic pots in triplicates (24 pots in total) and sown with 1.5 g of a grass seed mixture. The pots were stored in the laboratory next to a window in natural light, holding constant soil moisture level by manual irrigation with distilled water during April through May months.

3.4.2 Pelletized materials

Plant pot experiments with pelletized residues were performed in the similar manner as described above with some modifications, namely, 800 g of soil and soil mixed with 2% pellets (BFA4 or MFA4) was placed in plastic pots in triplicates (9 pots in total) and sown with 1 g of a grass seed mixture. The pots were placed under the artificial light for 12 h and the temperature between 13°C and 15°C. After five weeks pots were placed under the natural light for further two weeks, in order to apply higher temperatures and improve the plant growth (Paper V).

3.4.3 Plant biomass and element uptake

The plant shoots from the soil fertilization experiments with powdered and pelletized residues and their combinations were harvested after 7 weeks for biomass measurements and element concentration analysis. The plants were washed with double distilled water, dried for 72 h at 60°C, weighed for dry mass determination, then ground using a stainless steel grinder and analysed for chemical elements by the accredited laboratory ALS Scandinavia. Bulk soil was carefully separated from the rhizosphere for further analyses (Papers IV-V).

3.4.4 Soil pore water

All the pots were equipped with Rhizon soil moisture samplers (polymer, 10 cm length, Ø = 2.5 mm, average pore size, 0.1 µm). Soil pore water was collected right before harvesting the plants into vacuumed glass bottles for pH, EC and element analysis (Papers IV-V).

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3.5 Evaluation Methods

3.5.1 Analytical methods

The content of total solids (TS) in the materials was determined according to Swedish standard SS 028113 (SIS, 1981). The total element concentration in ashes and their mixtures was taken as a sum of six fractions from the sequential extraction test, except for the RDF fly ash, where the total amount of substances was determined by dissolution in aqua regia at the accredited laboratory ALS Scandinavia. The total N in the solid material was analyzed according to the standard ASTM D5373 by the accredited laboratory ALS Scandinavia. The concentrations of elements in solution were measured by inductively coupled plasma optical emission spectroscopy (ICP-OES, Perkin Elemer Otima 2000 DV). Dissolved organic carbon (DOC) was analyzed using a TOC-VCPH/CPN instrument (Shimadzu Corporation) according to European standard for water analysis of TOC and DOC (SS-EN 1484). The chloride (Cl) content was determined spectrophotometrically (AACE Quaatro, Bran+Luebbe, Germany).

Statistics. A two-sample t-test procedure (p<0.05) was applied to discriminate among the sample means.

3.5.2 Element extractions

Batch leaching test. A standard one-stage compliance batch leaching test (SS-EN 12457-4) at a liquid to solid ratio of 10 l/kg (L/S 10) was applied to estimate leachable concentrations of constituents in fresh and aged, granulated and pelletized residue mixtures and soil (Papers I-IV).

Sequential element extraction. Individual residues and materials, their mixtures, bulk soil and rhizosphere from powdered and pelletized fertilization experiments were subjected to the sequential extraction. Six steps were applied for element fractionation in 1 g of the sample according to the modified procedure adjusted to this study (Papers III-V).

3.5.3 Acid neutralisation capacity

A standard method SS-EN ISO 9963-1 (1996) was used for acid neutralisation capacity (ANC) determination was slightly modified (Papers I-II, V).by taking 1 g of ash suspended in 110 ml of de-ionized water and titrated with 0.1 M HCl, while stirring until the end-point pH 4.5 was reached.

3.5.4 Leaching potential calculation

The theoretical leaching of each element from the mixtures (Ct) was calculated as a sum of the leached concentration of an element in individual materials (Ca; Cb) adjusted to the percentage used in the mixture: Ct= (Ca · %) + (Cb · %) (Paper III). Then ratios of measured amounts of elements in the leachate and the theoretically calculated amounts of elements were calculated. Numbers below 1 indicate that the measured concentrations were lower than the calculated ones (Paper III).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

3.5.5 Mineralogical composition

The mineralogical composition of samples was determined qualitatively by X-ray diffraction using a Siemens D5000 X-Ray diffractometer (Paper I-II). Also X-ray diffraction data were recorded with a PANalytical Empyrean instrument, equipped with a PIXcel3D detector and a Cu LFF HR X-ray tube (Paper V).

Samples were examined with scanning electron microscopy (SEM) using a Kevex Quantum window and a Microspec WDX-3PC wave-dispersive analyser (Paper II).

3.5.6 Geochemical modelling

Geochemical equilibrium modelling was performed with PHREEQC-2 (Parkhurst and Appelo, 1999) (Paper II) and Visual MINTEQ ver. 3.0 softwares (Gustafsson, 2011) (Paper III) in order to identify potential solubility controlling minerals and to evaluate possible formation of clay minerals in the ashes.

3.5.7 Multivariate Data Analysis

The influence of the aging factors on the ANC and leaching of chemical compounds from the RDF fly ash was evaluated by multivariate data analysis (MVDA) with SIMCA-P+ ver. 11.5 (Eriksson, 2006) (Paper I). MVDA was also to the coefficients of variation (CV%), as indicators of the variation among replicates, to evaluate the reliability of the results and possible errors (Paper II).

3.5.8 Model evaluation

The computer software MODDE 9.0 (Eriksson et al., 2008) was used for Partial Least Squares (PLS) analysis of data acquired from the acid neutralisation capacity and leaching tests (Paper II).

4. Discussion

Considering environmental impact on future generations, the requirements for a landfill top cover are that it would be stable for ca. 1000 years. However, in practice such a long-term evaluation is impossible. Therefore, accelerated ageing experiments in the laboratory, which simulate long-term behaviour of fly ashes, may be a promising tool contributing to overcoming this practical obstacle.

4.1 Ageing of fly ash under various environmental conditions

Fly ashes used in a landfill top cover are subjected to the ageing processes that cause mineralogical transformations, effect chemical stability and changes in leaching behaviour (Papers I-II).

4.1.1 Mineralogical transformations in aged ashes

Ageing of ash in the long-term (31 months) laboratory experiment (Papers I-II) simulating inter alia conditions close to those found in a landfill top cover (20% CO2,

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65% RH, 30°C T), resulted in the transformation of comparatively soluble forms of oxides and hydroxides into less soluble carbonates. Hydration and carbonation were the main chemical reactions effecting the dissolution and precipitation of mineral phases in ashes during ageing (Papers I-II) (Figure 7).

Figure 7. Fresh and aged ash SEM images: a) and b) Fresh ash. c) Ash aged for 10 months under 0.038% CO2, 100% RH, 5°C with distilled water. d) and e) Ash aged for 22 months under 0.038% CO2, 100% RH, 5°C with leachate. f) and g) Ash aged for 31 months under 0.038% CO2, 30% RH, 60°C with distilled water. h) and i) Ash aged for 31 month under 20% CO2, 65% RH, 30°C with distilled water. All images were taken with 15 kV acceleration voltage at different magnifications.

Formation of carbonates can cause clogging of the ash pores thereby decreasing porosity directly related to permeability of a residue (Maurice and Lagerkvist 1998). Carbonation also stabilizes the material by binding trace elements into carbonates and binding particles together, which results in hardening and strengthening of the material and reduced leaching of trace elements from it (Chandler et al. 1997; Papers I-II). In particular calcite (calcium carbonate) was the main mineral phase that formed abundantly in the RDF fly ash aged under elevated CO2 conditions (Papers I-II).

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Hence, in a landfill top cover where CO2 concentration is higher than in the atmosphere, carbonates can easily form and partly control the leaching of trace elements such as Cu, Pb and Zn.

The geochemical equilibrium modelling indicated potential occurrences of various solubility-controlling mineral phases that only partly conformed to results of the XRD and SEM analysis (Papers I-II). For example, clay minerals were not detected by XRD (or SEM) analysis, possibly because they were present at levels below the threshold concentration of a mineral for XRD detection (≥ ca. 4%), and/or that clay minerals formed in the specimens were non-crystalline or poorly crystalline, and thus not detectable. There is also a possibility that no clay minerals were formed in any of the ashes during ageing.

4.1.2 Element solubility in aged ashes

Another important property of the studied fly ash is the acid neutralization capacity (ANC), which plays a substantial role in maintaining pH levels. The pH in turn is the most important factor governing the solubility of various mineral phases, heavy metals and trace elements in aged ashes (Chandler et al., 1997). The results of ANC analysis indicated that ashes used in a landfill top cover might have the ability to buffer and keep the pH around 4.5 for a longer period of time compared to fresh ash (Papers I-II). This may cause the carbonate dissolution and release of the bound trace elements e.g. Cu, Pb and Zn at pH below 6 (Baciocchi et. al., 2010). However, carbonates, particularly calcite (CaCO3) in RDF fly ashes, resist acidification by increasing the buffering capacity of ashes (Papers I-II). Consequently, the hazardous components immobilised in the ashes are not likely to be released due to the high buffer capacity, which will probably not be exhausted for 1000 or even 10000 years (Hirschmann and Förstner, 1997).

Both reaction time and level of CO2 under which fly ashes were aged reduced the pH, which in turn affected the leaching behavior of most soluble constituents. In general, leaching of Ba, Ca, Cl, Cr, Cu, Pb, K, Zn and Na decreased while that of Mg increased in aged ashes (Paper I-II). But fly ash exposed to the conditions similar to a landfill top cover liner (20% CO2, 65% RH, 30°C T and under the influence of leachate from upper soil layers) leached 50% less chlorides and 200 times less Pb compared to fresh ash (Paper II). Relative air humidity and the type of water used in the tests (distilled or leachate) did not cause any evident impact on the leaching behaviour.

Concentrations of Ba, Cr, Cu, DOC, Pb, Zn and SO4 in the leachates of ash aged under conditions similar to the landfill top cover were consistently below the limit values for accepting waste at landfills for non-hazardous waste (2003/33/EC, 2002) (Paper I). The concentrations of many other elements, e.g. Al, As, Cd, Co, Fe, Mn, Ni and S, in the leachates were below the instrument detection limits in most cases. Even though chloride leaching significantly decreased during ageing, concentrations of chlorides in most ash leachates remained above the leaching limit values.

Results of this study confirm that the leaching of potentially hazardous compounds from the liner material will be rather low (Tham and Andreas, 2008). Since a low permeability liner containing RDF fly ashes hinders the percolation of water through

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it, and thus the leaching of substances from it. Still, special care should be taken to reduce water contact with the surface of the compacted ash layer to avoid salt washout by mineral dissolution and thus preserving the overall stability of a liner.

4.2 Element availability in fly ashes used as soil fertilizers

Today EU policies encourage use of biofuel fly ashes on soil as an alternative to currently depleting mineral fertilizers. Contrary to MSWI and RDF fly ash, biofuel fly ash (BFA) from combustion of wood-based fuel is considered as clean and is readily used as nutrient-rich soil fertiliser in forestry (Demeyer et al., 2001; Pitman, 2006) provided it passes quality control requirements where the maximum allowable concentrations of certain elements (e.g. P, As, Pb, Cd and etc.) are defined (National Board of Forestry, 2002).

In another case, the use of MSWI fly ash on soil is limited, mainly because of the type of fuel incinerated, which may be hazardous wastes. Therefore potentially toxic elements concentrated in the MSWI fly ash may pose environmental risk for soil environment if such fly ash is applied on soil. However, it has been observed that element availability to leaching and plant uptake in soil often poorly correlates with the total element concentrations in materials (Chen et al., 2009). The residue mixture experiments demonstrated that solubility of potentially toxic elements in MSWI ash might be as low as that of biofuel ash, as shown by leaching tests of materials, despite differences in total element concentrations (Paper III).

Some concerns, however, remain. As nitrogen content in ashes may be too low to fulfil the plant demands, combining fly ash with N-rich biosolids or other materials is needed to balance the nutrients in potential fertilisers (Paper III). Indeed, combining ashes with biosolids had a positive effect on P and N availability as P and N solubility significantly increased compared to the fly ashes alone (Table 3-4 in Paper III). Furthermore, the mixing of residues had a notable impact on the solubility of several potentially toxic elements; the leaching of Pb in the combined fly ashes with other materials was lower than in the single ashes, but for Cd this had an opposite effect. Leaching of Cd from material mixtures increased between 8 and 50 times compared with that from ashes alone (Tables 3-4 in Paper III). Cadmium and Pb along with Hg and As are of particular interest since the use of these elements as well as their emissions is restricted in many countries due to their toxicity to animals and humans (Månsson et al., 2009). Cadmium, supplied from mineral fertilizers, is known to be one of the most problematic potentially toxic elements that tend to leach and accumulate in soil and plants (Eriksson and Helén, 2011). Therefore low leaching of potentially toxic elements would be an advantageous property of ash-based fertilisers. A further analysis of the reasons for the increased Cd mobility might help to adjust the proportions of the materials used in the mixtures.

Application of pelletized MSWI fly ash with biosolids on soil resulted in elevated total concentrations of As, Cd and Pb in soil (by 29%, 100% and 300%), but dissolved concentrations of these elements in pore water (0.08±0.04 mg/l, 0.004±0.001 mg/l and 0.006±0.003 mg/l respectively) (Figure 8), besides the As, were in the range of drinking water concentrations (0.005 mg/l of Cd and 0.01 mg/l of Pb) (2006/118/EC; 98/83/EC). Further, the concentrations of Cd and Pb in plant biomass were negligible regardless of the type of ash used (Table 4). Even applications

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of fly ash containing extremely high concentrations of Cd (400 mg/kg) were shown to have no effect on e.g. microflora in the humus layer of a coniferous forest (Perkiömäki et al., 2003). It appears likely that the plant uptake of Cd and Pb is counteracted by the availability of major nutrients and particularly phosphorus. The ability of P amendments to reduce Pb availability and phytoavailability is frequently observed in Pb contaminated soils (e.g. Hettiarachchi and Pierzynski, 2002). Similar observations are reported for Cd (Panwar et al. 1999; Brown et al., 2004). The suggested mechanism responsible for the low concentrations of Cd and Pb in the above-ground biomass is a P-induced decrease in metal translocation from roots to shoots (Chen et al., 2007; Qiu et al., 2011). Furthermore, P is considered to be a chemical analogue for As in soil (Adriano, 2001) and it might be expected that substantially higher P concentrations in the mixtures can suppress As uptake. This could be the reason for the observed higher uptake of As in soil amended with MSWI fly ash as the P/As ratio was lower in MSWI fly ash (5) compared to the biosolids (778) (Paper III). This suggests that to reduce the accumulation of potentially toxic elements in vegetation, ashes should preferably contain substantial amounts of soluble P, which can be achieved by mixing ash with biosolids. Moreover, application of Zn-rich residue mixtures to soil might further help to counteract Cd uptake by plants. Zinc is known as a chemical analogue of Cd, exhibiting antagonistic behaviour for plant uptake (Lee et al., 2004; Wang et al., 2011), possibly due to a larger ionic radius of Cd as compared to Zn.

High concentrations of chloride ions, on the other hand, have been shown to increase dissolved Cd concentrations and its plant uptake (Smolders et al., 1997). This might explain why Cd concentrations in soil containing MSWI-mixtures were higher and the Cd uptake by plants was greater compared to other mixtures (Paper V). In spite of this, Cd concentration in plants remained low (0.3±0.1 mg/kg).

Phosphorus is one of the primary plant nutrients, but in most soils it is relatively unavailable for plant uptake. A strong P fixation in soil is an important reason why only a fraction of applied P fertilizers are taken up by plants. Phosphorus may be strongly bound to Fe and Al phosphates (Ohno, 1992) or be adsorbed on Fe and Al oxyhydroxides (Ahn et al., 2001). Phosphorus availability depends on the incineration temperatures (Gray and Dighton, 2006). Phosphorus is commonly present in solid phase bound to insoluble basic oxides (Gray and Dighton, 2006) and are not in a water-soluble form in ashes. However, P applied in the form of pelletized ashes and biosolids had a positive effect on P uptake by plants (Table 4), despite the low dissolved P concentration in soil solution (Paper V).

Plants are capable of solubilizing some of the strongly bound P, e.g. to Fe oxides, through exudation of organic acids (Jan et al., 2013) and by doing so increase P uptake even at lower availability. High P accumulation in plants might also be the reason for the observed low dissolved P concentration in soil containing pelletized residues (Paper V).

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Figure 8. The pH and elements in the soil pore water after 7 weeks of experiment where powdered (black) and pelletized (grey) fly ash and other materials were used. BioS – biosolids, BFA – biofuel fly ash, MFA – municipal solid waste incineration fly ash, BFA4 – BFA combined with BioS, MFA4 – MFA combined with BioS.

Table 4. Concentration (mg/kg) of elements in the biomass (n=3, ± STDVE). BioS – biosolids, BFA – biofuel fly ash, MFA – municipal solid waste incineration fly ash, BFA4 – BFA combined with BioS, MFA4 – MFA combined with BioS.

Ele

men

t

Soil

Soil+

Bio

S

Soil+

BFA

Soil+

B

ioS+

BFA

Soil+

C

aK2PO

7

Soil+

C

aKPO

4

Soil4

*

Soil4

+

BFA

4

Soil4

+

MFA

4

P 1883±411 3297±235 2317±55 4380±522 4039±2533 3667±289 5953±264 5300±376 5033±372

Al 119±45 174±8 167±133 117±52 235±179 229±17 58±30 87±23 25±17

As <0.5 <0.5 <0.5 <0.5 0.9±0.5 <0.5 <0.5 <0.5 4.3±1.8

Ba 41±2 17±2 42±8 23±3.41 5.2±3.8 15±4.3 115±24 55±9.7 51±8

Cd <0.04 0.05±0.002 0.08±0.01 0.09±0.03 <0.04 0.05±0.01 0.2±0.03 0.08±0.01 0.3±0.1

Pb <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3

Zn 21±3 35±6 40.5±2.6 59±3 22±13 17.4±3.5 53±3 48.3±2.3 47.5±6.3 *-italic indicates experiment with pelletized fly ash and biosolids.

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Evelina Brännvall, Waste Science & Technology, LTU 2013

Figure 9. Plant biomass production in the plant pot experiment with powdered (black) and pelletized materials (grey). BioS – biosolids, BFA – biofuel fly ash, MFA – municipal solid waste incineration fly ash, BFA4 – BFA combined with BioS, MFA4 – MFA combined with BioS.

Figure 10. Biomass development in the powdered residue mixtures. BioS – biosolids, BFA – biofuel fly ash, MFA – municipal solid waste incineration fly ash.

Figure 11. Biomass development in the soil and pelletized residue mixtures. BFA4 – biofuel fly ash combined with biosolids, MFA4 – municipal solid waste incineration fly ash combined with biosolids.

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Fly ash contains a significant amount of calciumsilicate and aliuminosilicate phases. Dissolution of these phases may lead to the increased concentrations of Ca and Si (which are considered to have a positive impact on soil) and Al (which may have an undesirable toxic effect on plants). But Al is rarely a problem in neutral soils, as it can easily react with phosphates, sulphates and other organic and inorganic ligands at pH>5 that would keep dissolved Al in non-toxic concentrations (Delhaize and Ryan, 1995; Ma et al., 2001). Therefore application of slightly alkaline mixtures on acidic soil would be beneficial in reducing potential Al toxicity to plants by keeping the soil slightly alkaline (Figure 8) (Papers IV-V). Indeed, in all soil mixtures containing fly ashes, concentrations of dissolved Al in soil pore water were below instrument detection limits. While in unamended soil, the dissolved Al concentration was the highest (0.048 mg/l) (Figure 11) yet within the tolerable limits for plants (<1.6 g/l) (Poschenrieder et al., 2008). Furthermore, Al accumulation in plants grown on the soil containing MSWI fly ash was 70% lower than in soil containing biofuel fly ash (Table 4).

The purpose of combining fly ashes with biosolids was to improve the nutrient balance and chemical properties of the fertilizer, and by this to increase the biomass production in the vegetation layer of a landfill top cover. Despite positive changes in chemical properties, such as decreased availability of potentially toxic elements and increased supply of nutrients, combination of biofuel fly ash with biosolids had negative effect on biomass development (Figures 9-11). The plant biomass was lower in soil containing biofuel fly ash mixed with biosolids compared to unamended soil in both experiments (with powdered and pelletized materials) (Papers IV-V). Such results were unexpected and the reasons are not quite clear. Too short time given for plants to grow, changes in water balance in soil caused by these amendments could be possible reasons. Longer-term studies are needed to elucidate possible benefits of soil fertilization with fly ash and biosolids combinations.

Prediction of element availability in fly ash combined with other materials is not as straight forward as could be expected (Paper III). Theoretical calculations of leaching potential showed the differences between the measured and calculated leaching potential of elements (Table 6 in Paper III). This indicates that materials most likely interacted with each other through various geochemical processes, such as dissolution, precipitation, complexation with organic matter and sorption to metal hydroxides, causing significant changes in element availability.

Element availability for plants showed that application of both MSWI and biofuel fly ashes do not increase element accumulation in plants. Therefore, total concentrations of elements in fly ash do not directly reflect their behaviour and potential impacts on soil and plants. Responsible application of MSWI ashes is, however, warranted in order to avoid element accumulation in soil and elevation of background values over time.

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5. Conclusions

Application of fly ash in a landfill top cover has advantages and disadvantages:

RDF fly ash exposed to the conditions found in a landfill top cover (20% CO2, 65% RH, 30°C T) will lead to the chemical and mineralogical transformations that result in reduced leaching of most of the elements studied here. Only concentrations of Cl in the leachates may be an issue, because they still exceed the leaching limit values; nevertheless the leaching of this element in aged ash decreased by 50% compared to fresh ash. Geochemical modelling showed that clay minerals, which favour the immobilization of heavy metals, could form in ageing RDF fly ashes. Consequently, a landfill top cover containing these ashes can be expected to remain chemically stable over a long period of time. Based on the observations, RDF fly ash is considered as a suitable material to be used in a landfill liner.

Element availability changed in fly ashes combined with other materials. Nutrients (N and P) availability improved, but also undesirable availability of potentially toxic elements (As and Cd) significantly increased.

MSWI fly ash pelletized with biosolids and applied on soil resulted in the increase of total concentrations of As, Cd and Pb in that soil, nevertheless concentrations of these elements, aside from As, dissolved in soil pore water were as low as in natural and drinking water. Furthermore, the concentrations of Cd and Pb in plant biomass were negligible regardless of the type of ash used. Therefore the availability and not the total concentrations of elements might be the more accurate property for defining the fly ash suitability for land applications. Therefore, analysing fly ash impact on element distribution in soil, not only total concentrations but also other tests such as solubility of element in soil pore water and availability for plants should be included.

Based on element availability for plants all studied ashes could be considered suitable for land application. But doses to be applied on soil should be adjusted to the type of ashes to avoid accumulation of potentially toxic elements in soil over time.

6. Outlook

The experimental studies showed that fly ash used in construction and land applications can be beneficial for saving natural resources. However, some issues warranting further research were identified in the study.

Each type of fly ash, originating from combustion of different types of fuels and incinerators, has different properties and further research should focus on analysing other fly ashes and other material combinations in order to augment the results obtained in this work.

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The presence of potentially harmful organic compounds or substances such as dioxins and furans should also be investigated.

Because fly ash is strongly affected by various environmental conditions and element availability changes over time, the life-cycle and seasonal-cycles of plants and their element-uptake should be investigated. In addition, a broader range of plant species should be investigated to elucidate the changes in element availability in ash-fertilised soil and the potential environmental impact over time.

7. References

98/83/EC. Council Directive 98/83/EC on the quality of water intended for human consumption.

2000/76/EC. Directive 2000/76/EC of the European Parliament and of the Council of 4 December 2000 on the incineration of waste. http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CONSLEG:2000L0076:20001228:EN:PDF.

2003/33/EC. Council Decision 2003/33/EC of 19 December 2002 establishing criteria and procedures for the acceptance of waste at landfills pursuant to Article 16 of and Annex II to Directive 1999/31/EC. Official Journal of the European Communities 16.1.2003(L11): 27-49.

2006/118/EC. Directive 2006/118/EC of the European Parliament and of the Council of 12 December 2006 on the protection of groundwater against pollution and deterioration. ANNEX 3. http://ec.europa.eu/environment/water/water-framework/groundwater/pdf/com_swd_annex_iii.pdf. Accessed on 20130917.

Adriano, D.C. 2001. Trace Elements in Terrestrial Environments: biogeochemistry, bioavailability, and risks of metals. 2nd ed, Springer-Verlag, New York. 867 p.

Ahn, C., Mitsch, W.J, Wolfe, W.E. 2001. Effects of recycled FGD liner material on water quality and macrophytes of constructed wetlands; a mesocosm experiment. Wat Res 35, 633–642.

Almansouri, M., Kinet, J. M., & Lutts, S., 2001. Effect of salt and osmotic stresses on germination in durum wheat (Triticum durum Desf.). Plant and Soil, 231(2), 243-254.

Andreas, L., Herrmann, I., Lidström-Larsson, M. and Lagerkvist, A., 2005 Physical properties of steel slag to be reused in a landfill cover. pp:451–457, CISA, S. Margherita di Pula, Cagliari, Italy; 3 – 7 October 2005.

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