Suitability of Fly Ash For

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% CO 2 , 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
1
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),
Evelina Brännvall, Waste Science & Technology, LTU 2013

2
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 SiO 2 , Al 2 O 3 and CaO, K 2 O,

Na 2 O, MgO and Fe 2 O 3 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).
3
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.
Biofuel
Group/ Mineral name Formula RDF MSWI
(wood)
Fresh Aged
1 2 3 4 5
CARBONATES
Calcite CaCO 3 17; 3 1; 11; 13; 25; 2;11;12 16; 18; 21; 15
Fairchidite K 2 Ca(CO 3 ) 2 21; 25
Huntite Mg 3 Ca(CO 3 ) 4 15
Magnezite MgCO 3 13
Natrite Na 2 CO 3 8
Vaterite CaCO 3 3 12
CLAY MINERALS
Illite KAl 3 Si 3 O 10 (OH) 2 1
Syngenite K 2 Ca(SO 4 )2H 2 O 22 2 16
CHLORIDES
Blixite Pb 2 Cl -x (O,OH) 2x 26
Cotunnite PbCl 2 26
1; 5; 8; 9; 11-14; 19; 25; 2;
Halite NaCl 17; 4; 3
11; 12
Hydrocalumite Ca 8 Al 4 (OH) 24 (CO 3 )(Cl) 3; 4 1; 12;
Hydrophilite CaCl 2 6
Sylvite KCl 4; 3 14 18; 21
Zinc Chloride ZnCl 2 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 Ca 3 Al 2 O 6 15
Calcium titanite CaTiO 3 1
Corundum Al 2 O 3 12
Grossite CaAl 4 O 7 5
Hematite Fe 2 O 3 7 1; 13; 2
Lime CaO 12; 25 21
Magnetite Fe 3 O 4 1
Minium Pb 3 O 4 1
Periclase MgO 7 21
Rutile TiO 2 1; 2
Ulvöspinel Fe 2 TiO 4 1; 2
PHOSPHATES
Aluminum phosphate AlPO 4 15
Hydroxiapatite Ca 5 (PO 4 ) 3 (OH) 21
SILICATES
Akermanite Ca 2 Mg(Si 2 O 7 )
Albite NaAlSi 3 O 8 16; 15
Amorphous glass 1 16
Anorthite CaAl 2 Si 2 O 8 5
Augite Ca 3 Na 3 Mg 3 FeAl1.6 Si 7 O 24 1
Calcium silicate hydrate Ca 1.5 SiO 3.5 ·xH 2 O 7 11
Cristobalite SiO 2 2
Diopside CaMgSi 2 O 6 1

4
1 2 3 4 5
Enstatite (Mg,Fe)SiO 3 1
Feldspar 25
Ferrosilicate, magnesian (Fe,Mg)SiO 3 15
Forsterite (Mg,Fe) 2 SiO 4 1
Garnet Ca 3 (Al,Fe) 2 (Si,P) 3 O 12 1
Gehlenite Ca 2 Al 2 SO 7 3 1; 11; 12; 25; 2; 12; 13 15
Gismondite CaAl2Si2O8 · 4H2O 8
Hatrurite Ca 3 SiO 5 1
Kalsilite KAlSiO 4 1
Kilchoanite Ca 3 Si 2 O 7 10
Larnite Ca 2 SiO 4 1; 9
Merwinite Ca 3 Mg(SiO 4 ) 2 21
Microcline K 2 AlSi 3 O 8 16
Mullite Al 2 O 3 ·SiO 2 16
Nepheline Na 3 KAl 4 Si 4 O 16 1
Plagioclase (Na,Ca)((Si,Al)AlSi 2 O 8 ) 21
Quartz SiO 2 6; 4; 24; 3 1; 11-13; 19; 25; 2; 8; 11; 16; 18; 21; 15
12
Sanidine KAlSi 3 O 8 1; 5 21
Sodalite Na 4 Al 3 Si 3 O 12 Cl 1
Tobermorite Ca 5 (OH) 2 SiO 16 ·4H 2 O 1
SULPHATES
Allenite MgSO 4 ·5H 2 O 5
Alunite KAl 3 (SO 4 ) 2 (OH) 6 1
Anhydrite CaSO 4 6; 17; 7; 3 1; 8; 11-14; 19; 23; 25 21
2 11 12
Aphthitialite K 3 Na(SO 4 ) 2 15
Bassanite CaSO 4 ·0.5H 2 O 1; 2
Caracolite Na 3 Pb 2 (SO 4 ) 3 Cl 1; 2
Ettringite 3CaO·Al 2 O 3 ·3CaSO 4 ·32H 2 O 4; 3 1; 20 15
Gordaite NaZn 4 (SO 4 )(OH) 6 Cl(H 2 O) 6 1; 2
Gypsum CaSO 4 ·2H 2 O 17 1; 11
SULPHIDES
Marcasite FeS 2 1
Pyrite FeS 2 1
1
Bayuseno 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).
5
Table 2. Mineral changes that occur during ageing of fly ash (adapted from Donahoa, 2004).
Process Mineral changes Chemical reaction

Hydration Anhydrite to gypsum: CaSO 4 +2H 2 O→CaSO 4 ·2H 2 O
Ettringite formation 3CaSO 4 +Ca 3 Al 2 O 6 +32H 2 O→Ca 6 Al 2 (SO 4 ) 3 (OH)
12 · 26H 2 O
Lime to portlandite: 2CaO+H 2 O→2Ca(OH) 2
Solution/ Dissolution of gypsum: CaSO 4 →Ca2++SO 4 2-
Dissolution
Hydrolysis Dissolution of glass: Me-Al-Si-O
(schematic reaction) glass+H 2 O+H+→Me++Al(OH) 3 (am)+SiO 2 (am)
Carbonation Portlandite to calcite: Ca(OH) 2 +CO 2 →CaCO 3 +H 2 O
Ettringite to calcite and Ca 6 Al 2 (SO 4 ) 3 (OH) 12 ·26H 2 O + 3CO 2 →
gypsum 3CaCO 3 +3(CaSO 4 ·2H 2 O)+Al 2 O 3 H 2 O+25H 2 O
Oxidation Magnetite to hematite: 2Fe 3 O 4 +0.5O 2 →3Fe 2 O 3
Precipitation Ferric hydroxide: Fe3++3OH-→Fe(OH) 3
Ettringite 3CaSO 4 +Ca 3 Al 2 O 6 +32H 2 O→Ca 6 Al 2 (SO 4 ) 3 (OH)
12 · 26H 2 O
Adsorption Heavy metals on oxides: Fe-OH+Me2+→Fe-OMe++H+
Co- Ideal solid solution Fe(OH) 3 (s)+Me2+→Me(OH) 2 (s)+Fe3++OH-
precipitation between Fe(OH) 3 and
Me(OH) 2 :
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.

6
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 CO 2 in water.
The gas below the liner consists primarily of CH 4 , N 2 , CO 2 and O 2 . The typical
concentration (by volume) of carbon dioxide in landfill gas is between 20 and 50%
(Lagerkvist, 2003). The absorption of CO 2 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
7
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?

8
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).
9
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, CaK 2 P 2 O 7 and CaKPO 4 , 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 (CO 2 %), 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).

10
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, CO 2 (%) 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% CO 2 and 80% N 2
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).
11
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).

12
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 (C t ) was calculated as a
sum of the leached concentration of an element in individual materials (C a ; C b )
adjusted to the percentage used in the mixture: C t = (C a · %) + (C b · %) (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).
13
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% CO 2 ,

14
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% CO 2 , 100% RH, 5°C with distilled water. d) and e) Ash aged for 22 months
under 0.038% CO 2 , 100% RH, 5°C with leachate. f) and g) Ash aged for 31 months under
0.038% CO 2 , 30% RH, 60°C with distilled water. h) and i) Ash aged for 31 month under
20% CO 2 , 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 CO 2 conditions (Papers I-II).
15
Hence, in a landfill top cover where CO 2 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 (CaCO 3 ) 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 CO 2 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% CO 2 , 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 SO 4 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

16
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
17
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).

18
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.
BioS+BFA
Soil+BioS
CaK 2 PO 7
Soil+BFA
CaKPO 4
Element
MFA4
Soil4+
Soil4+
Soil4*
BFA4
Soil+
Soil+
Soil+
Soil
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.
19
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.

20
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.
21
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% CO 2 , 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.

22
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.
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Paper #14.

Suitability of Fly Ash For

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Suitability of Fly Ash for

Construction and Land Applications

Department of Civil, Environmental and Natural Resources Engineering

Division of Geosciences and Environmental Engineering

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

I cordially thank my supervisor Associated Professor Jurate Kumpiene whose patience,

I would like to express my very great appreciation also to:

The financial support provided by the EU Regional Development Fund Objective 2

Luleå, 2013 October

Paper V Evelina Brännvall, Martin Wolter, Rolf Sjöblom, Jurate Kumpiene.

Other papers by the author not included in the thesis:

Brännvall E, Andreas L, Sjöblom R, Kumpiene J. & Lagerkvist A. 2011. Ageing of

Brännvall E, Andreas L, Diener S, Tham G, Sjöblom R. & Lagerkvist A. 2010.

Diener S, Andreas L, Brännvall E & Lagerkvist A 2010. Evaluation and discussion of

Brännvall E, Andreas L, Diener S, Tham G, Lagerkvist A 2009. Influence of accelerated

ANC Acid neutralization capacity

BFA Biofuel fly ash

CEC Cation exchange capacity

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

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

MVDA Multivariate data analysis

PCA Principal Component analysis

PLS Partial Least Square projections to latent structures

STDVE Standard deviation

SEM Scanning electron microscopy

XRD X-ray diffraction

1. Introduction and Background ......................................................................... 1

1. Introduction and Background

1.1 Properties of fly ashes

MSW is very heterogeneous, consisting of diverse unburned organic and inorganic

Evelina Brännvall, Waste Science & Technology, LTU 2013

Figure 1. Ternary diagram showing relative proportions of SiO 2 , Al 2 O 3 and CaO, K 2 O,

Mineralogical composition of MSWI as well as RDF fly ashes consists of mixtures of

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

Evelina Brännvall, Waste Science & Technology, LTU 2013

Process Mineral changes Chemical reaction

1.2 Application of fly ash in a landfill top cover

Evelina Brännvall, Waste Science & Technology, LTU 2013

Evelina Brännvall, Waste Science & Technology, LTU 2013

2. The Scope of the Thesis

The following questions cover the focus of the thesis:

3. Materials and Methods

3.1.1 Fly ash

Figure 3. Refuse-derived-fuel fly ash.

3.1.2 Other materials and substrates

3.2 Ageing of fly ash

Evelina Brännvall, Waste Science & Technology, LTU 2013

Factor Low Intermediate High

3.3 Material mixtures

3.4 Soil fertilization

3.4.1 Powdered materials

3.4.2 Pelletized materials

3.4.3 Plant biomass and element uptake

3.4.4 Soil pore water

Evelina Brännvall, Waste Science & Technology, LTU 2013

3.5 Evaluation Methods

3.5.1 Analytical methods