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Caratterizzazione mineralogica e chimica delle ceneri pesanti provenienti dalla combustione dei rifiuti

De Matteis, Chiara · 2023

Abstract

Waste generation is, today, a hot topic, strongly linked to environmental problems. Wastes have been produced since the dawn of civilization: the increasing world population and global development occur together with an increasing production of man-made objects, which at the end of their life become waste. Increasing industrial production in the last two centuries pose the problem of their disposal, and in more recent times of their management. Waste management is nowadays a global topic together with that of climatic changes and georesource shortage: it is foreseen to become more and more critical in response to the improvement in life standard in developing countries and in the increased consumption of raw materials. Waste management is a complex issue, aiming to reduce the production and to recycle and reuse the waste, avoiding or minimising any dispersion in the environment. The goal in waste management can be summarised in the mantra “from waste to resource”. Prominent among improvements and innovations concerning waste management are Waste-to-Energy (WtE) plants, systems that generate energy from the combustion of solid waste, mostly municipal. In WTE plants the solid waste is burned, with a positive energy balance, coming from the combustion of the wastes, which is used for the energy production. However, like any anthropogenic activity, this process generates wastes: bottom ashes and fly ashes. Bottom ashes are the residual ashes in the bottom part of the combustion chamber, whereas fly ashes are the residuals blowing out from the chamber. Also, the bottom ashes (BA) from Municipal Solid Waste Incinerator (MSWI) can be recycled. Due to their physical and chemical-mineralogical characteristics, BA can be used as a secondary source of raw material or recycled into construction and cementitious materials. However, their recycling may be compromised due to the presence of Potential Toxic Elements (PTE), i.e. chromium, lead, and zinc, as their release may be harmful to the environment and human health. The aim of this thesis is to provide a systematic and in-depth study on the BA, with special focus on the medium-fine fraction (< 4mm). This work has two goals, the mineralogical characterization of the bottom ashes and the assessment of their potential release. In both, special attention was paid to PTE. The goals are closely related, as the information on the mineralogical phases hosting the PTE is a key point for interpreting and assessing the potential release of the BA in the environment. In this work BA from 5 WtE plants in Northern Italy were sampled and sorted by grain size. Each sampling was analysed by Thermo Gravimetric Analysis (TGA), X-Ray Powder Diffraction (XRPD), X-Ray Fluorescence (XRF), Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM - EDS) and X-ray Absorption. Synchrotron based Near Edge Spectroscopy (XANES) and XAF analyses were further conducted, to obtain a full chemical and mineralogical information. The potential release of BA was investigated on particle sizes < 4mm by leaching test and sequential extraction procedure. From the results obtained, we found that several elements exceed the legal limits (chlorides, copper) already in the leaching test, where extraction is conducted only with ultrapure water at neutral pH. The relation between grain size, composition, and leaching potential were assessed in the ashes to discuss the potential of grain size sorting in high value applications of them. This thesis is organised as follows. In the first chapter the concept of waste is introduced, together with the figures on global and national waste production. The operational procedures and different types of waste-to-energy plants are described, and the characterization of bottom ashes is introduced. A literature review on the current state of the art on chemical, physical and mineralogical characteristics, together with the possible environmental problems and reuses of the bottom ashes is addressed. In the second chapter the materials and methods used in this work are outlined, in what they are common to this investigation. Specific aspects are further discussed in the sub-chapters 3.1, 3.2, 3.3 and 3.4. The chapter 3 shows the results and discussion of the different topics addressed in this investigation. It is divided in four subchapters, each corresponding to a paper published, submitted, or in preparation. In the subchapter 3.1 the paper “Particle size and PTE speciation in MSWI bottom ash”, published in 2021 in the journal Sustainability, is reported, giving a mineralogical characterization of the bottom ashes, with different grain size, from the Parma WtE. In the sub-chapter 3.2 the version submitted to the journal Waste Management of the paper “Toward a deep characterization of bottom ashes from municipal solid waste incineration: new data from 5 plants of Northern Italy” is reported. The bottom ashes from the WtE of Piacenza, Torino, Forlì-Cesena and Ferrara, together with a new sampling from the WtE from Parma were examined. The mineralogy, geochemistry and leaching behaviour of the ashes were compared, and the trend outlined in the sub-chapter 3.1 were discussed in their generalization. In the sub-chapter 3.3 the pre-submission version of the paper “PTE speciation in Bottom Ashes from Municipal Solid Waste Incinerator: a combined SEM-EDS, XRF and XANES by synchrotron radiation study”, is reported, to be submitted to the Journal of Hazardous Materials. This investigation discusses the mineralogy of the PTE elements, combining a SEM-EDS information on the mineralogy of the host phases, with synchrotron based XRF and XANES data, to outline the local distribution and mineralogy of the PTE elements at concentrations of the order of few ppm. In the sub-chapter 3.4 the results of a sequential extraction procedure on the bottom ashes from Parma and Piacenza are reported, and discussed together with a PCA analysis of the correlations between elements and grain size in the bulk material and in the leached products. A new protocol for the sequential extraction procedure in bottom ashes is proposed. Finally, the fourth chapter reports the general conclusions from this work with a final focus on problems in the recycle of the bottom ashes.

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Caratterizzazione mineralogica e chimica delle ceneri pesanti provenienti dalla combustione dei rifiuti

Author: De Matteis, Chiara
Publisher: Università degli studi di Parma. Dipartimento di Scienze chimiche, della vita e della sostenibilità ambientale
Year: 2023
Source: https://www.repository.unipr.it/bitstream/1889/5358/6/PHD_THESIS_DE%20MATTEIS%20CHIARA_3103_DEF.pdf
UNIVERSITÀ DI PARMA
Dipa imen o di Scienze Chimiche, della Vi a e della Sos enibili à Ambien ale
Co so di Do o a o in Scienze della Te a
Ciclo XXXV (2019 – 2022)
MINERALOGICAL AND CHEMICAL
CHARACTERIZATION OF BOTTOM ASHES
FROM WASTE INCINERATION
Ca a e izzazione Chimica e Mine alogica delle cene i pesan i
p o enien i dalla combus ione dei i iu i
Tu o :
P o . Ma io T ibaudino
P o .ssa Luciana Man o ani
Coo dina o e:
P o . Ma co Ro e i
Candida a:
Do .ssa Chia a De Ma eis
Depa men o Chemis y, Li e Sciences and En i onmen al Sus ainabili y
Ph. D in Ea h Sciences
XXXV cycle (2019 – 2022)
MINERALOGICAL AND CHEMICAL
CHARACTERIZATION OF BOTTOM ASHES
FROM WASTE INCINERATION
Supe iso s:
P o . Ma io T ibaudino
P o .ssa Luciana Man o ani
Coo dina o :
P o . Ma co Ro e i
Candida e:
Do .ssa Chia a De Ma eis
Table o con en s
PREFACE ....................................................................................................................................... 1
1 INTRODUCTION......................................................................................................................... 4
1.1 AGE OF HUMANS ........................................................................................................... 4
1.2 GLOBAL WASTE PRODUCTION .................................................................................... 5
1.3 EUROPEAN AND ITALIAN WASTE MANAGEMENT .................................................... 6
1.4 WASTE TO ENERGY PLANTS ........................................................................................... 10
1.5 BOTTOM ASHES: COMPOSITION AND PROBLEMS ....................................................... 13
1.5.1 Physical cha ac e iza ion ................................................................................................. 14
1.5.2 Chemical and mine alogical cha ac e iza ion .................................................................... 14
1.5.3 Reco e y and ecycle o Bo om Ashes ............................................................................... 20
1.5.4 Mine alogy, PTE elemen s and en i onmen al conce n: aims o his hesis .......................... 23
2. MATERIALS AND METHODS ................................................................................................. 25
2.1 DESCRIPTION OF THE WASTE-TO-ENERGY PLANT ..................................................... 25
2.1.1 Pa ma W E plan (I en g oup) .......................................................................................... 25
1.6.2 Piacenza W E plan (I en g oup) ....................................................................................... 25
1.6.3 To ino W E plan (I en g oup) .......................................................................................... 25
1.6.4 Fe a a W E plan (He a g oup) ....................................................................................... 25
1.6.5 Fo lì-Cesena W E plan (He a g oup) ............................................................................... 26
2.2 SAMPLING.......................................................................................................................... 26
2.3 SAMPLE PREPARATION ................................................................................................... 26
2.4 GRAIN SIZE ANALYSIS ..................................................................................................... 26
2.5 THERMO GRAVIMETRIC ANALYSIS (TGA) .................................................................... 26
2.6 SEM-EDS OBSERVATIONS AND ANALYSIS ..................................................................... 27
2.7 X-RAY POWDER DIFFRACTION (XRPD) ANALYSIS ....................................................... 28
2.8 X-RAY FLUORESCENCE (XRF) ANALYSIS ...................................................................... 29
2.8.1 XRF spec oscopy: con en ional sou ce ............................................................................. 29
2.8.2 µ - XRF spec oscopy: synch o on adia ion ..................................................................... 30
2.9 X-RAY ABSORPTION SPECTROSCOPY (XAS) ................................................................. 31
2.10 LEACHING TEST .............................................................................................................. 34
2.11 SEQUENTIAL EXTRACTION PROCEDURE (SEP) .......................................................... 35
2.12 ATOMIC ABSORPTION SPECTROSCOPY (AAS) ANALYSIS ......................................... 38
2.13 IONIC CHROMATOGRAPH (IC) ANALYSIS ................................................................... 38
2.14 INDUCTIVELY COUPLED PLASMA – MASS SPECTROMETRY (ICP-MS) ANALYSIS . 38
2
2.15 STATISTICAL ANALYSIS ................................................................................................ 39
3 RESULTS AND DISCUSSION .................................................................................................... 40
3.1 MINERALOGICAL CHARACTERIZATION OF BOTTOM ASHES ................................... 40
3.1.1 Pa icle size and Po en ial Toxic Elemen s specia ion in Municipal Solid Was e Incine a ion
(MSWI) Bo om Ash ................................................................................................................ 40
3.2 COMPARISON BETWEEN W E PLANTS IN NORTHERN ITALY..................................... 59
3.2.1 G ain size and mine alogical cons ains on leaching in he bo om ashes om municipal solid
was e incine a ion: a compa ison on 5 plan s om No he n I aly ............................................... 59
3.3 PTE SPECIATION: COMBINED SEM-EDS ANALYSIS, XRF AND XANES BY
SYNCHROTRON RADION STUDY .......................................................................................... 81
3.3.1 PTE specia ion in Bo om Ashes om Municipal Solid Was e Incine a o : a combined SEM-
EDS, XRF and XANES by synch o on adia ion s udy .............................................................. 81
3.4 SEQUENTIAL EXTRACTION PROCEDURE AND ENVIRONMENTAL CONCERN ....... 106
4 CONCLUSIONS ....................................................................................................................... 112
REFERENCES ............................................................................................................................ 115
WEB REFERENCES ................................................................................................................... 127
APPENDIX I
.............................................................................................................................. 128
APPENDIX II.............................................................................................................................. 132
APPENDIX III ............................................................................................................................ 133
APPENDIX IV ............................................................................................................................ 134
APPENDIX V .............................................................................................................................. 136
APPENDIX VI ............................................................................................................................ 138
APPENDIX VII ........................................................................................................................... 139
APPENDIX VIII .......................................................................................................................... 144
APPENDIX IX ............................................................................................................................ 149
APPENDIX X .............................................................................................................................. 154
APPENDIX XI ............................................................................................................................ 159
APPENDIX XII ........................................................................................................................... 160
APPENDIX XIII .......................................................................................................................... 161
APPENDIX XIV .......................................................................................................................... 162
APPENDIX XV ........................................................................................................................... 163
APPENDIX XVII ........................................................................................................................ 165

1
PREFACE
Was e gene a ion is, oday, a ho opic, s ongly linked o en i onmen al p oblems. Was es ha e been
p oduced since he dawn o ci iliza ion: he inc easing wo ld popula ion and global de elopmen
occu oge he wi h an inc easing p oduc ion o man-made objec s, which a he end o hei li e
become was e. Inc easing indus ial p oduc ion in he las wo cen u ies pose he p oblem o hei
disposal, and in mo e ecen imes o hei managemen . Was e managemen is nowadays a global
opic oge he wi h ha o clima ic changes and geo esou ce sho age: i is o eseen o become mo e
and mo e c i ical in esponse o he imp o emen in li e s anda d in de eloping coun ies and in he
inc eased consump ion o aw ma e ials.
Was e managemen is a complex issue, aiming o educe he p oduc ion and o ecycle and euse he
was e, a oiding o minimising any dispe sion in he en i onmen . The goal in was e managemen can
be summa ised in he man a “ om was e o esou ce”.
P ominen among imp o emen s and inno a ions conce ning was e managemen a e Was e- o-
Ene gy (W E) plan s, sys ems ha gene a e ene gy om he combus ion o solid was e, mos ly
municipal. In WTE plan s he solid was e is bu ned, wi h a posi i e ene gy balance, coming om he
combus ion o he was es, which is used o he ene gy p oduc ion. Howe e , like any an h opogenic
ac i i y, his p ocess gene a es was es: Bo om Ashes and Fly Ashes. BA a e he esidual ashes in he
bo om pa o he combus ion chambe , whe eas FA a e he esiduals blowing ou om he chambe .
Also, BA om Municipal Solid Was e Incine a o (MSWI) can be ecycled. Due o hei physical and
chemical-mine alogical cha ac e is ics, BA can be used as a seconda y sou ce o aw ma e ial o
ecycled in o cons uc ion and cemen i ious ma e ials. Howe e , hei ecycling may be comp omised
due o he p esence o Po en ial Toxic Elemen s (PTE), i.e. ch omium, lead, and zinc, as hei elease
may be ha m ul o he en i onmen and human heal h.
The aim o his hesis is o p o ide a sys ema ic and in-dep h s udy on he BA, wi h special ocus on
he medium- ine ac ion (< 4mm). This wo k has wo goals, he mine alogical cha ac e iza ion o
he BA and he assessmen o hei po en ial elease. In bo h, special a en ion was paid o PTE. The
goals a e closely ela ed, as he in o ma ion on he mine alogical phases hos ing he PTE is a key
poin o in e p e ing and assessing he po en ial elease o he BA in he en i onmen .
In his wo k BA om 5 W E plan s in No he n I aly we e sampled and so ed by g ain size. Each
sampling was analysed by The mo G a ime ic Analysis (TGA), X-Ray Powde Di ac ion (XRPD),
X-Ray Fluo escence (XRF), Scanning Elec on Mic oscopy wi h Ene gy Dispe si e Spec oscopy
(SEM - EDS) and X- ay Abso p ion. Synch o on based Nea Edge Spec oscopy (XANES) analyses
we e u he conduc ed, o ob ain a ull chemical and mine alogical in o ma ion.
2
The po en ial elease o BA was in es iga ed on pa icle sizes < 4mm by leaching es and sequen ial
ex ac ion p ocedu e. F om he esul s ob ained, we ound ha se e al elemen s exceed he legal
limi s (chlo ides, coppe ) al eady in he leaching es , whe e ex ac ion is conduc ed only wi h
ul apu e wa e a neu al pH.
The ela ion be ween g ain size, composi ion, and leaching po en ial we e assessed in he ashes o
discuss he po en ial o g ain size so ing in high alue applica ions o hem.
This hesis is o ganised as ollows. In he i s chap e he concep o was e is in oduced, oge he
wi h he igu es on global and na ional was e p oduc ion. The ope a ional p ocedu es and di e en
ypes o was e- o-ene gy plan s a e desc ibed, and he cha ac e iza ion o BA is in oduced. A
li e a u e e iew on he cu en s a e o he a on chemical, physical and mine alogical cha ac e is ics,
oge he wi h he possible en i onmen al p oblems and euses o he BA is add essed.
In he second chap e he ma e ials and me hods used in his wo k a e ou lined, in wha hey a e
common o his in es iga ion. Speci ic aspec s a e u he discussed in he sub-chap e s 3.1, 3.2, 3.3
and 3.4.
The chap e 3 shows he esul s and discussion o he di e en opics add essed in his in es iga ion.
I is di ided in ou subchap e s, each co esponding o a pape published, submi ed, o in
p epa a ion. In he subchap e 3.1 he pape “Pa icle size and Po en ial Toxic Elemen specia ion in
Municipal Solid Was e Incine a o (MSWI) Bo om Ash”, published in 2021 in he jou nal
Sus ainabili y, is epo ed, gi ing a mine alogical cha ac e iza ion o he BA, wi h di e en g ain
size, om he Pa ma W E plan . In he sub-chap e 3.2 he e sion submi ed o he jou nal F on ie s
o he pape “Towa d a deep cha ac e iza ion o bo om ashes om municipal solid was e
incine a ion: new da a om 5 plan s o No he n I aly” is epo ed. The BA om he W E plan s o
Pa ma, Piacenza, To ino, Fo lì-Cesena and Fe a a we e examined. The mine alogy, geochemis y
and leaching beha iou o he ashes we e compa ed, and he end ou lined in he sub-chap e 3.1
we e discussed in hei gene aliza ion. In he sub-chap e 3.3 he e sion submi ed o he jou nal
Science o To al En i onmen o he pape “Po en ial Toxic Elemen s specia ion in Bo om Ashes
om Municipal Solid Was e Incine a o : a combined SEM-EDS, XRF and XANES s udy”, is epo ed.
This in es iga ion discusses he mine alogy o he PTE, combining a SEM-EDS in o ma ion on he
mine alogy o he hos phases, wi h synch o on based µ-XRF and XANES da a, o ou line he local
dis ibu ion and mine alogy o he PTE a concen a ions o he o de o ew ppm. In he sub-chap e
3.4 he esul s o a sequen ial ex ac ion p ocedu e on he BA om Pa ma and Piacenza a e epo ed,
and discussed oge he wi h a co ela ion be ween elemen s and g ain size in he bulk ma e ial and in
he leached p oduc s. A new p o ocol o he sequen ial ex ac ion p ocedu e in BA is p oposed.
3
Finally, he ou h chap e epo s he gene al conclusions om his wo k wi h a inal ocus on
p oblems in he ecycle o he BA.
4
1 INTRODUCTION
1.1 AGE OF HUMANS
Humani y is now a dominan geological ac o , as human ac i i ies induce g ea , mul iple and
i e e sible changes on Ea h. The s udy o hese human-associa ed changes led o he sugges ion ha
we should no e e o he p esen ime as pe aining o he Holocene epoch bu o a new geological
epoch called he “An h opocene” (C u zen, 2002; S e en, 2021; T ischle , 2016; Zalasiewicz e al.,
2011). In 2000, he i s o p opose he idea o he An h opocene we e he a mosphe ic chemis Paul
Joze C u zen and he limnologis Eugene Filmo e S oe me ; since hen, he geological communi y
has begun o ake an inc easing in e es in his issue, analysing scien i ic e idence leading o a
de ini ion o he An h opocene and es ablishing he “An h opocene Wo king G oup” (T ischle ,
2016).
O he scien i ic b anches (biology, ecology, e hology) also began o s udy he co ela ion be ween
en i onmen al changes and human ac i i ies and he idea o An h opocene is now accep ed and
sha ed by mos o he scien i ic communi y. Howe e , he scien i ic deba e is s ill open on
es ablishing he “s a ing poin ” o his new epoch.
Figu e 1.1.1 Compa ison o he cu en Geologic Time Scale wi h wo al e na i es. (Lewis & Maslin, 2015)
Fo example, in Figu e 1.1.1 he cu en Geological Time Scale 2012 (a) is compa ed wi h wo
possible scena ios. In he i s al e na i e (b) he An h opocene Epoch di ec ly ollows he Holocene
11
• umes expulsion: he umes a e channelled in o a chimney and expelled in o he a mosphe e
a a empe a u e o abou 120 °C;
• ash collec ion: he ashes ob ained om he combus ion o was e and he solid pa icles
ob ained om lue gas pu i ica ion a e collec ed in wo sepa a e lines, s o ed and sen o
land ills o ecycling companies.
The mos a iable pa o was e- o-ene gy plan s is he u nace. Th ee echnologies a e used (Figu e
1.4.2):
• G a e u nace echnology: his echnique is mos commonly used. The was e en e s h ough
he uel chu e and hen i is pushed on o he g a e by a eed mechanism. The uel hen mo es
along he (usually) sloping g a e. The uppe uel su ace-laye is exposed o adia ion om
he e ac o y s uc u es o he u nace and he lames, o med by he ola ile gases abo e he
uel laye , and hea s up and d ies. Subsequen ly, as he empe a u e o he uel laye ises, he
uel de ola ilises as i mo es o wa ds on he g a e. When he igni ion empe a u e is eached,
combus ion s a s, p omo ed by he p ima y ai om he bo om sec ions: li le ai is supplied
in he d ying sec ion, and he emaining p ima y ai is adjus ed in he a ious supply duc s
benea h he g a e acco ding o he p og ess o combus ion in he cen al sec ion o he bed.
The combus ion on o med mo es downwa ds in o he bed agains he ai low, while he
bed mo es o wa ds (Leckne , 2015). The combus ion empe a u e is be ween 750 and
1000°C.
• Fluised bed echnology: in con as o he uel bed on he g a e, he uel is in oduced o an
ine luidized bed, consis ing o sand-like pa icles o abou 0.5 mm in size, and mixes wi h
his bed ma e ial and he emaining ashes om he was e. The ad an age o he luidized bed
is he ho bed, which has a g ea he mal ine ia o he uel pa icles o bu n in a con olled
and he mally s able en i onmen . This ad an age is no en i ely e ec i e in was e
combus ion, hough, because he ola ile pa o he uels ends o bu n in he eeboa d abo e
he bed in any case. The bed empe a u e is usually 850° C, bu i could be highe as long as
he bed does no sin e . The p ima y luidiza ion ai is in oduced h ough nozzles,
adi ionally co e ing he en i e bo om o he u nace, he ‘‘dis ibu o pla e’’. This leads o
accumula ion o la ge and dense objec s in he bo om egion, o igina ing om he was e,
which e en ually p e en s p ope ai dis ibu ion, dis u bs luidiza ion, and a ou s
agglome a ion. The e o e, luidized bed combus ion o was e has he epu a ion o equi ing
well so ed was e (Leckne B., 2015).
• Ro a ing u nace echnology: he o a y u nace, o o a y kiln, is used o d ying and o he
ope a ions in ol ing g anula ma e ials. In he ield o was e ea men , i is mos equen ly

12
employed o combus ion o haza dous was e. A o a y u nace consis s o a cylind ical s eel
essel, o 10 m in leng h and a ew me es diame e , inclined by a ew deg ees om he
ho izon al plane. Inside, he essel is p o ec ed by e ac o ies. The cylind ical s eel essel
es s upon olls and is o a ed a a speed be ween 0.05 and 2 e olu ions pe minu e. The uel
is ed a one end and he ashes lea e a he o he end. D ying, de ola iliza ion, and combus ion
ake place, while he uel is o a ed and mixed, some imes e en enhanced by in e nals. The
leng h and diame e o he cylinde , as well as i s o a ion speed, slope, and in e nals, all
in luence he esidence ime o he uel pa icles. This abili y o con ol he esidence ime
e en in was es o di e en inpu is he main ad an age o he de ice. Howe e , he
incine a ion o en does no come o comple ion and usually an a e bu ne combus ion
chambe is needed (Leckne B., 2015).
Figu e 1.4.2 The mos common con e sion de ice o was e, he e shown in he o m o combus o s: (a)
g a e u nace, (b) luized bed and (c) di ec ly hea ed o a y u nace (Leckne B., 2015)
A e an ini ial cooling phase, bo om ashes a e sc eened manually o mechanically o emo e
o e sized unbu ned esidues. In addi ion, he e ous me al ac ion is emo ed wi h o e head
magne ic sepa a o s and he non- e ous me al ac ion is emo ed by Eddy cu en . Subsequen ly,
he ma e ial is s o ed on si e awai ing aging.
As men ioned abo e, om he combus ion o was e no only ene gy is ob ained bu also esidual
ashes. The ashes, which a e also a was e, can be classi ied on he basis o i s size and haza dousness:
• Fly Ashes (FA): hei mass ep esen s 2% -5% o he incine a ed was e. The FA a e he solid
pa icles ha a e eleased wi h he combus ion umes and a e emo ed a e he pu i ica ion
p ocess. Due o he high concen a ion o PTE, he FA a e classi ied as haza dous was e (EWC
13
code 19.01.13 *: ly ash con aining haza dous subs ances) and o his eason hey canno be
ecycled wi hou p e- ea men and a e usually collec ed and s o ed in speci ic land ills (Zhu
J. e al., 2020; Qiu e al., 2017; D.Lgs 152/06).
• Bo om Ashes (BA): BA a e one o he majo by-p oduc s ob ained du ing municipal solid
was e incine a ion in was e- o-ene gy plan s; hei mass is 20% o he incine a ed was e. Once
he incine a ion p ocess is comple e, he BA a e h own in o a ank ull o wa e o apid
cooling. The BA a e classi ied as non-haza dous was e (EWC code 19.01.12: bo om ash and
slag o he han hose in 19.01.11 *).
1.5 BOTTOM ASHES: COMPOSITION AND PROBLEMS
The BA a e made up o di e en ac ions which, hanks o he non-haza dous na u e o he unbu ned
ma e ial, can be ecycled becoming a esou ce. The ac ions can be di ided as:
• glass (soda-lime glass), coming om domes ic i ems such as bo les and glasses. The amoun
o glass is highly dependen on he p esence o a selec i e collec ion o u ban was e.
• Syn he ic ce amics, de i ed om clay-based ma e ials (e.g. iles and b icks), po celain and
conc e e.
• Pa amagne ic me als, which ep esen a 2-5 w %; usually hey o igina e om s eel and i on
pieces oxidised in he incine a ion u nace. Mine al phases such as magne i e (Fe3O4),
hema i e (Fe2O3) and wues i e (FeO) a e cha ac e is ic o he BA ine ac ion ha is no
emo ed by he magne ic sepa a o .
• Mine als, such as eldspa s calci e and qua z may ha e a na u al o igin ( hey a e common in
soil and ock), bu hey a e also common componen s in ce amics o building ma e ials as
well as majo wea he ing p oduc s in MSWI BA (calci e).
• Diamagne ic me als, which ep esen 10-12 w % o he BA weigh . They a e mainly
ep esen ed by aluminium and coppe , and end o be concen a ed in he ines ac ion (below
1 mm).
• Unbu ned o ganic ma e which comes om he pa ial combus ion o ood esidues, pape ,
ab ic and bone agmen s (Chimenos e al., 1999).
The composi ion o BA a ies o e ime and om coun y o coun y, due o he di e ences in
li es yle and was e ecycling p ocesses o a coun y. To no e, i is ex emely he e ogeneous and may
change, also in he same plan , depending on he di e en mix o was es bu ned each day; mo eo e ,
e en wi hin he same mix, he e a e seasonal di e ences (Dhi e al., 2017). This he e ogenei y in he
was e incoming ma e ial gi es ise o a a ia ion in composi ions om g ain o g ain in he BA.
Mo eo e , some inhomogenei y in he combus ion empe a u e adds u he he e ogenei y in he
14
he modynamic condi ions o local equilib ia. I mus be emphasised ha , despi e his he e ogenei y,
some phases a e commonly ound (Chimenos e al., 1999; Fo eza e al., 2004; Inkaew e al., 2016;
Lynn e al., 2016; John Chandle e al., 1997c; Alam e al., 2019; Ty e , 2013; Lam e al., 2010;
Ca iglia e al. 2019; Man o ani e al. 2021).
This complex chemical and mine alogical composi ion gi es ise o nume ous scien i ic ques ions
ega ding hei euse and non-haza dousness. O e he pas 20 yea s, many esea ch g oups s udied
BA by implemen ing a mul idisciplina y app oach me ging he con ibu ions o en i onmen al
geology, geochemis y, and enginee ing.
The p ope ies o he BA can be di ided in o chemical and physical p ope ies. These p ope ies a e
essen ial o a managemen o he was e: any p oposed ecycle mus ake in o accoun he chemical
and physical eac i i y o he ashes, o op imise he indus ial p oduc ion, o assess and imp o e he
pe o mance o he ecycled p oduc , and o p edic i s long- e m use in e ms o pollu ion and
du abili y.
1.5.1 Physical cha ac e iza ion
The mine al ac ion o BA is ypically ligh o da k g ey and is a g anula ma e ial (al hough i may
also con ain la ge used lumps).
The physical cha ac e iza ion o he BA in ol es, p elimina y o o he in es iga ions, an analysis o
he g ain size dis ibu ion. The g ain size dis ibu ion is mos impo an in he ecycling in he
cons uc ion indus y, and, as discussed in he ollowing, may be di e en in di e en incine a o s.
The pa icle size dis ibu ion is ypical o well-g aded ma e ials and gene ally con o ms wi h ha o
sandy g a el, wi h a con en o 40mm o e size pa icles commonly below 5% by o al mass as well
as a low po ion o ines (<63 mic on) (As up e al 2016, Izquie o e al. 2011).
B oadly speaking we ha e ha abou 45 % o he mass o he BA is made by g ains la ge han 5 mm,
whe eas abou 35 % o he mass alls in an in e media e g ain size be ween 1 and 5 mm; ine-g ained
ma e ial be ween 0.1 and 1 mm make abou 10 % in weigh , whe eas he emaining 10 % o he BA
shows a g ain size less han 0.1 mm (Dou X. e al., 2017; Šyc e al., 2018Hube e al., 2020). O he
physical p ope ies ha can desc ibe BA a e ep esen ed by he loss o igni ion, usually 1-3% (Lynn
e al., 2017) i.e. weigh pe cen age los when hea ed o 4 h a 500 °C, speci ic g a i y, bulk densi y
( /m3) ha is ypically 1.200-1.800 kg/m3, and wa e abso p ion (%).
1.5.2 Chemical and mine alogical cha ac e iza ion
The composi ion o he BA changes wi h he inpu ma e ial, he combus ion echnology, and he pos
combus ion wea he ing. The inpu ma e ial depends on local li es yle was e p oduc ion, bu also by
15
selec i e collec ion o household was e. Selec i e collec ion makes i possible o eco e ma e ials
o which ecycling op ions a e a ailable and economically iable. I was obse ed ha , whe e
sepa a e collec ions we e ca ied ou , glass and pape /ca dboa d ac ion sen o incine a ion ell by
10% and 8% espec i ely, while he p opo ion o o he ma e ials (e.g. ex iles) inc eased by 30%. A
lowe silicon con en in he o BA was ound a e he in oduc ion o selec i e collec ion, which
dec eased he inpu in bo le glass o he incine a o (del Valle-Ze meno e al., 2017).
The composi ion o he ashes changes also as a unc ion o he incine a ion echnology: incine a ion
is a complex echnique o mas e because i in ol es se e al essen ial pa ame e s as he s o age and
composi ion o incoming was e, he eeding o he u nace, he combus ion empe a u e, he
igni abili y o he was es, he oxygen supply and he p ocess ime in he u nace. These pa ame e s
ha e impo an e ec s in he mine alogical composi ion o he ashes and in he p esence o o ganic
ma e . The same inpu ma e ial, bu ned wi h di e en u nace echnologies, o a ing, luidized bed
o g a e, will p oduce a di e en mine alogical composi ion o he ashes. As men ioned be o e, he
g a e u nace is he mos used in household was e incine a ion plan s.
Also, he cooling a e incine a ion a ec s he mine alogical composi ion o he ashes. The cooling
can be wi h wa e o ai . The wa e -cooling p ocess is he mos used and p oduces a apid cooling
oge he wi h chemical eac ions be ween BA and wa e , loss o me als due o oxida ion o adhesion
o mine al ma e o me als. Ai cooling gene a es dus ha equi es special ea men bu a oids he
chemical in e ac ion wi h wa e .
The ma u a ion p ocesses can educe he en i onmen al pollu ion po en ial o he ma e ial, as
he modynamically uns able compounds e ol e in o mo e s able seconda y compounds in he
p esence o ca bon dioxide, bu also o oxygen o wa e . Usually BA a e exposed o ai o 1 o 12
mon hs. Ma u a ion changes he chemical and mine alogical composi ion, abso bing CO2 o o m
ca bona es, mos ly calci e, and mois u e apou , o o m cemen mine als like e ingi e.
Fo all hese ac o s he ashes a e e y he e ogeneous e en om he same incine a ion plan .
Howe e , despi e hese a iables, he e a e simila i ies among he di e en chemical composi ions
epo ed in he li e a u e (Table 1.5.2.1).
Gene ally speaking, he majo oxides in BA a e CaO, SiO2, Al2O3 and Fe2O3 ha ep esen be ween
60 and 80 w % o he chemical composi ion. The mino elemen s a e Cu, Zn, C , Sb, Mo, Co and Ni,
and make up abou 1.5–2.0 w % along wi h 1.5–5.0 w % o chlo ides and sul a es, he ac ual amoun
depending also on he size ac ion o BA (Alam e al. 2020). Fo each elemen sys ema ic di e ences
a e obse ed as a unc ion o he g ain size (Ca iglia e al., 2019; del Valle-Ze meno e al., 2017;
Logino a e al., 2019; Hube e al., 2019). Among he majo elemen s, (Si, Ca, Al, and Fe) Si con en
16
inc eases wi h g ain size, while Ca ollows an opposi e end. Al, Fe, Mg and K show de ini e end
as epo ed in (Ca iglia e al., 2019; Funa i e al., 2015; Logino a e al., 2019).
Fo mino and ace elemen s, on he o he hand, g ea e a iabili y has been epo ed bu in he las
li e a u e da a published he highe concen a ions a e ound in he ine ac ion (Ca iglia e al., 2019;
Funa i e al., 2015; Logino a e al. 2019). The poin will be discussed in he ollowing in mo e de ail.
These elemen s combine oge he o o m c ys alline and amo phous silico-alumina es. In ac , BA
a e cha ac e ised by e ac o y (ce amic, me als una ec ed by he combus ion p ocess) and mel (slag
mine als o med du ing incine a ion) phases. Quenched BA a e o med by agglome a ed ma e ial,
con aining ca bona es and hyd a ed phases (Inkaew e al., 2016). Usually, glass/amo phous phases
o m he pa icle co e, while on he pa icle su ace hyd a ion p oduc s a e ound as calcium silica e
hyd a es (C-S-H), F iedel’s sal /hyd ocalumi e, e ingi e, gypsum and calci e. The cooling inside he
ank can be a sou ce o chlo ides and sulpha es due o he p esence o Cl- and SO42- in he quenching
wa e (I o e al., 2008).
In gene al, glass and semi- used me allic ma e ial is p esen in la ge amoun s in he coa se pa icle
sizes, while slags a e p esen in g ea e amoun s in he ine g ain size classes. The mos common
mine alogical phases a e (i) silica es (qua z, melili es, eldspa s), (ii) ca bona es (calci e, a e i e),
(iii) oxides (magne i e, hema i e, co undum), and (iiii) hyd a ed phases ypical o cemen i ious
ma e ials (hyd ocalumi e, po landi e, e ingi e, s a lingi e). Fo u he de ails see Table 1.5.2.2,
om Syc e al. (2020). In addi ion o hese main phases, a high con en o amo phous ma e ial is also
p esen (Alam e al., 2019; Be olini e al., 2004; Bayuseno & Schmahl, 2010; Ca iglia e al., 2019;
Yao e al., 2012). Mine alogical composi ion also a ies as a unc ion o g ain size: o example, he
amo phous con en is highe in la ge g ains while ca bona es a e p esen in g ea e amoun s in he
ine g ains.

17
Majo Elemen s
Concen a ion
ange (min-max)
in mg/kg
Po en ial oxic
elemen s
Concen a ion
ange (min-max)
in mg/kg
Ra e ea h
elemen s
Concen a ion
ange (min-max)
in mg/kg
Pla inum me al
g oup
Concen a ion
ange (min-max)
in mg/kg
o he p ecious
and c i ical
elemen s
Concen a ion
ange (min-max)
in mg/kg
Al
14000 – 79000
Ba
69 – 5700
Sc
1.3 – 22
P
0.074 – 0.53
Ag
0.2 – 36.9
Ca
8600 – 170000
Cd
0.3 – 70
La
2 – 30
Pd
0.03 – 1.8
Au
0.1 – 2.2
Fe
3100 – 150000
Cu
190 – 25000
Ce
11 – 51
I
0.0007 – 0.007
Sb
7.6 – 430
K
660 – 16000
C
20 – 3400
P
1.1 – 10
Rh
< 0.030
Be
1.2 – 6
Mg
240 – 26000
Mo
2.5 – 280
Nd
4 – 37
Ru
< 0.01
Co
6 – 350
Mn
77 – 3200
Ni
7.0 – 4300
Sm
0.93 – 5
Ga
7 – 24
Na
2200 – 42000
Pb
75 – 14000
Eu
0.25 – 2.6
Ge
0.78 – 2.7
P
440 – 10500
Se
0.05 – 10
Gd
0.88 – 5
In
< 1.7
Si
4300 – 308000
Sn
2 – 470
Tb
0.18 – 3
Nb
2 – 14
Ti
2783 – 7479*
Tl
0.0077 – 0.23
Gy
0.54 – 3
Ta
2.5 – 14
Cl
3644 – 37633
V
16 – 120
Ho
0.11 – 0.45
W
10 – 320
S
1310 – 16808
Zn
10 – 20000
E
0.31 – 2
Li
2 – 29*
Tm
0.01 – 0.18
Yb
0.31 – 5
Lu
0.02 – 0.23
Table 1.5.2.1: some li e a u e da a on he chemical composi ion o BA (modi ied om As up e al. 2016 and Hjelma e al. 2013)
18
Mine al phase
Chemical o mula
Unquenced BA
Quenced BA
Wea e ed BA
qua z
SiO2
h, i
b, e, , g, i
a, c, d, e,
c is obali e
SiO2
g
a, g
gehleni e
Ca2Al2SiO7
h, i
b, e, , g, i
a, e, , g
ake mani e
Ca2MgSi2O7
b, e
a, e
alkali eldspa s
(K,Na)(Al,Si)3O8
b, c (albi e),g
g
plagioclase eldspa s
NaAlSi3O8-CaAl2Si2O8
e, i
b, e, i
e
calcium py oxene
Ca(Mg,Fe)Si2O6
b, g
g
wollas oni e
CaSiO3
b, , g
, g
lime
CaO
e, i
b
po landi e
Ca(OH)2
c, g
magne i e
Fe3O4
e
e, , g
a, e, , g
hema i e
Fe2O3
h, i
i, , g
d, , g
wüs i e
FeO
, g
, g
calci e
CaCO3
h, i
e, i, , g
a, c, d, e, , g
goe hi e
FeO(OH)
d
co undum
Al2O3
e
e
gibbsi e
Al(OH)3
d
anhyd i e
CaSO4
c, e, g
d, g
gypsum
CaSO4 · 2H2O
a, g
hyd ocalumi e
Ca2Al(OH)6Cl1-x(OH)x 3H2O
, i
e
iedel’s sal
Ca2Al(OH)6Cl · 2H2O
i
e ingi e
Ca6Al2(SO4)3 (OH)12 · 26H2O
a, c, d, e
Table 1.5.2.2 mos common mine alogical phases iden i ied in BA. Re e ences: a) (Ze enbe gen e al.,
1998); b) (Eusden e al., 1999); c) (Chimenos e al., 2003); d) (Pian one e al.. 2004); e) (Bayuseno and
Schmahl. 2010); ) (Wei e al., 2011); g) (San os e al., 2013); h) (Bou salas. 2015); i) (Inkaew e al., 2016).
The nega i e co ela ion ha exis s be ween g ain size and ca bona es, bu also be ween g ain size
and hyd a ed phases, can be explained h ough a g ea e eac i i y o he ine g ains o he wea he ing
p ocess, as ca bona es and hyd a ed phases a e a p oduc o hyd a ion. We may compa e he chemical
composi ion o he a e age con inen al c us and ha o bo om ashes om municipal solid was e
incine a o s (MSWI), much in o ma ion on he human ac i i y p oduc s can be ob ained. Figu e
1.5.2.1(a) ep esen s he a e age composi ion o he oxides o common elemen (mo e an 1w %) in
MSWI BA ( om Djiks a e al. (2019), Hjelma e al. 2013 and his wo k) s he composi ion o he
19
a e age con inen al c us ( om CRC Handbook 2016). In Figu e 1.5.2.1 (a) is clea ly isible ha
mos abundan elemen s in BA (Al, Fe, Si, Ti, K and Na) a e e y close o ha o he con inen al
c us . Only wo elemen s show s ong en ichmen in BA, Ca and P; also loss on igni ion (LOI) con en
in BA is highe espec o he a e age c us . Despi e he case o Ca and P, he a e age composi ion
con i ms ha mine al was es homogenise he p oduc s o indus ial ac i i y o ob ain some hing close
in composi ion o he na u al con inen al c us .
Figu e 1.5.2.1 A e age composi ion o majo (a) and mino (b) elemen s in BA ( om Dijks a e al., (2019),
Hjelma e al. 2013 and his wo k) s con inen al c us composi ion ( om CRC Handbook 2016).
Figu e 1.5.2.1(b) epo s mino elemen s a e aged in he MSWI BA espec o he con inen al c us .
A i s g oup o elemen s, among which Co, Z , Li, H , Ti, Rb, F, V, Mn, S , Ga, U, Th shows an
a e age composi ion in BA e y close o he ea h con inen al c us while a second g oup made by
Cl, Zn, Cu, S, Pb, B , Mo and Sn, show a signi ican en ichmen in BA, be ween one and wo o de s
o magni ude.
By some espec he chemical p ocesses eco ded BA could be simila o hose in high empe a u e
geochemis y. The o e all composi ion is no a om ha o he global ea h, and he empe a u es
a e in he ange o he geological high empe a u e p ocesses; a combus ion chambe can be compa ed
wi h na u al high empe a u e sys ems. The di e ence lies in he ex eme he e ogenei y o he inpu
ma e ial. Du ing he incine a ion we obse e in di e en g ains mul iple equilib ia due o local
composi ional and empe a u e he e ogenei ies. A he local g ain size scale he high empe a u e
eac ions can be in e p e ed as indica ing he achie emen o a leas he p og ess o a he modynamic
20
equilib ium, obeying o he Gibbs phase ule, whe eas a he bulk scale his ob iously does no occu .
The mul iphase, mul iple equilib ia lead o weal h o phases e en in he g ains whe e he high
empe a u e glass and c ys als a e bes p ese ed. Mo eo e , un eac ed e ac o y ma e ial and low
empe a u e wea he ing induce u he mine alogical complexi y.
1.5.3 Reco e y and ecycle o Bo om Ashes
In o de o imp o e he p ope ies o MSWI BA physically o chemically, o ob ain a be e ma e ial
o applica ion o o educe he leaching concen a ion o con aminan s om MSWI BA and lowe i s
en i onmen al isk po en ial, se e al ea men s ha e been p oposed. Today mos plan s a e equipped
wi h magne ic sepa a o s and non- e ous sepa a o s o he ecycling o pu e me als such as i on o
aluminium. F om an economic poin o iew, he ecycling o me als p o ides a inancial bene i o
he company in addi ion o ob aining a cleane s ony ma e ial. Some au ho s (Biganzoli & G osso,
2013; Biganzoli e al., 2012) epo ed ha he eco e y le el o me als is limi ed by hei pa icle size.
A ocal poin deba ed in he las yea s ega ds he ex ac ion and immobilisa ion o con aminan s as
sal s o hea y me als, and hei ex ac ion wi h wa e o chemical washing. Howe e , i was no
ecommended o wash he MSWI BA due o he la ge amoun o gene a ed was e wa e o chemical
eagen s (Lin e al., 2011; Yang e al., 2012). Gene ally, he ea men s on BA MSWI a e ma ched
wi h hei applica ions, such as using bo om as in conc e e and meanwhile, he binde s in he conc e e
ha e an immobilisa ion e ec on he hea y me als in he BA.
The pollu ing po en ial o BA is a key ac o in deciding on i s use as well as i s s o age in app op ia e
si es. Ac ually, each coun y has de ined a egula o y and legisla i e amewo k on he managemen
o BA wi h a iew o iden i y eco e able and non- eco e able ma e ials. The cons uc ion sec o
emains, o all Eu opean coun ies, he main e-use o BA, in o de o limi he use o non- enewable
na u al esou ces. Un o una ely, he non-uni o mi y o Coun y s anda ds ac as an obs acle in he
ull alo isa ion o hese ma e ials. The EU legisla ion can be ound in Di ec i e 2010/75/EU on
indus ial emissions bu each coun y has i s na ional egula ions implemen a ion. B ie ly, any was e
incine a ion plan ope a ed in a membe s a e needs o adhe e o he minimum equi emen s se ou
in he abo e men ioned di ec i e in which he p incipal equi es a e o minimise he amoun and
po en ial haza d o combus ion esidues, and o ha e ecycling s a egies in place, a e ha ing
assessed BA physical and chemical p ope ies, as well as hei pollu ing po en ial, including he
de e mina ion o he o al soluble ac ion and soluble ac ion o hea y me als.
The Eu opean Union equi es Membe S a es o ca y ou leaching es s acco ding o he s anda ds
EN 12457/1 2002, EN 12457/2 2002, EN 12457/3 2002, and EN 12457/4 2002, wi h a liquid- o-solid
(L/S) a io anging om 2 o 10 l/kg. I he BA espec s hese s a emen s wi hin he Communi y o
27
a quan i y o ma e ial equal o 3 -5mg was su icien o pe o m he analysis. TGA we e conduc ed
by means o a Pe kin Elme 8000 ins umen equipped wi h a P -c ucible a a hea ing a e o 10
°C/min in he empe a u e ange 35°C – 800 °C. All he measu emen s we e un unde a cons an lux
o d y ai a mosphe e (30 mL/min).
2.6 SEM-EDS OBSERVATIONS AND ANALYSIS
In a p elimina y s ep, se e al BA g anules chosen in he Pa ma W E plan chosen in he g ain size
be ween 8 and 16 mm, o be in es iga ed in he pa icle size cha ac e iza ion pape , and be ween 0.5
and 1 mm o be in es iga ed o he pape ocussed on XRF-XANES mine al cha ac e iza ion. The
g ains we e embedded in epoxy esin s abs, cu longi udinally. A e a p elimina y op ical
obse a ion, by a pola ised s e eomic oscope BX51, OLYMPUS, Scanning Elec on Mic oscopy
(SEM) wi h Ene gy Dispe si e X-Ray Spec oscopy (EDX) analysis was done.
Scanning Elec on mic oscopy was used o de e mine he mic oscopic s uc u e and composi ion o
he phases which a e p esen in he BA. The elec on mic oscopy exploi s he in e ac ions ha occu
be ween an inciden elec on beam and he a oms in he sample by e u ning mo phological and
chemical in o ma ion (Figu e 2.6.1).
Figu e 2.6.1 Scheme o elec on-ma e in e ac ions a ising om he impac o an elec on beam on o a
sample (www. jl-mic oanaly ic.de/en/)
The analyses we e done using he SEM image ob ained om backsca e ed elec ons, oge he wi h
EDS poin o map analysis. A compa ison wi h op ic mic oscope images was done o highligh he
co espondence be ween composi ional and op ical inhomogenei ies, om he images ob ained by
backsca e ed elec ons and SEM – EDS mapping.

28
The SEM – EDS analyses we e pe o med a :
• Dipa imen o di Scienze Chimiche, della Vi a e della Sos enibili à Ambien ale (Uni e si à di
Pa ma) by a Scanning Elec on Mic oscope coupled wi h Ene gy Dispe si e Sys em (SEM-
EDS) JSM IT300LV Jeol 6400 equipped wi h an Ox o d EDX mic op obe. Mic op obe
analysis was pe o med wi h ope a ing condi ions 20 o 25 kV and 1.2 mA cu en , ~1µm
beam diame e and 75 s coun ing ime;
• Dipa imen o di Scienze della Te a (Uni e si à di To ino) by a JEOL JSM-IT 300LV
Scanning Elec on Mic oscope, equipped wi h Ox o d INCA Ene gy 200 EDS SATW
de ec o (WD 10, KV 15), a 15 kV, 1.2 mA cu en and 1µm beam diame e .
All da a collec ed we e p ocessed using he AZTEC so wa e (Ox o d ins umen s, 2006)
2.7 X-RAY POWDER DIFFRACTION (XRPD) ANALYSIS
X – Ray Powde Di ac ion was used o he iden i ica ion and quan i ica ion o he phases in he
samples. I was done on all g ain sizes, be o e u he analyses and ea men s. The phase
de e mina ion was done ia powde di ac ion, using he DIFFRAC.EVA so wa e, whe eas he
quan i a i e assessmen was done by Rie eld analysis o he di ac ion pa e ns and he GSAS – II
package. The samples we e g ound in an aga e mo a in o de o ob ain a homogeneous powde (<
0.063mm). A 10% by weigh s anda d (Al2O3 o Si) was also placed in each sample o pe o m
quan i a i e analyses a a la e ime o assess he deg ee o c ys allini y o he sample and he amoun
ela i e o each iden i ied mine alogical phase.
The measu emen s we e conduc ed a :
• Dipa imen o di Scienze Chimiche, della Vi a e della Sos enibili à Ambien ale (Uni e si à di
Pa ma) using a B agg-B en ano B uke 2D Phase Di ac ome e , wi h θ – θ geome y, Cu
Kα adia ion, 30 kV and 10mA and a solid-s a e de ec o ;
• Dipa imen o di Scienze della Te a (Uni e si à di To ino) using a B agg-B en ano Rigaku
Mini lex 600 Di ac ome e , wi h θ – 2θ geome y, Cu Kα adia ion, 40 kV - 15 mA,
mul is ip de ec o (128 s ip) and Kβ il e on inciden beam;
The di ac ion pa e ns collec ed we e iden i ied using he B uke so wa e DIFFRAC.EVA and he
C ys allog aphy Open (COD) and PDF-2005 da abases. The iden i ica ion was based on he i wi h
posi ion and in ensi y o he main di ac ion peaks. P oblems in iden i ica ion o phases wi h lowe
concen a ion came om he complexi y o he di ac ion pa e ns, due o he numbe o
mine alogical phases in he BA, and he consequen peak o e lapping. Mo eo e , he in ensi y o he
di ac ion pa e n was g ea ly educed by he p esence o glass and amo phous unbu ned o ganics.
29
A u he bias was ha he posi ion and in ensi y o he main di ac ion peaks, in phases showing
solid solu ions like plagioclase and melili e, was shi ed om hose in he e e ence da abase.
By his espec , we can conside ully iden i ied only phases wi h mo e han 1-2 w % p esence in he
sample.
Quan i a i e analysis was done by means o he Rie eld me hod. The Rie eld e inemen pe o ms
he analysis o he measu ed di ac ion p o ile by modelling he c ys al s uc u e, uni cell and
ela i e abundance o he c ys alline phases iden i ied in he di ac ion pa e n. The backg ound,
scale ac o and sample ela ed peak b oadening a e modelled as well, whe eas ins umen al
pa ame e s, like wa eleng h, ze o posi ion, and ins umen al peak shape a e de ined by an
ins umen al ile, bu can also modelled i necessa y (Rie eld, 1967 and 1969; Bish & Pos , 1989).
The quan i a i e analysis o he di e en c ys alline phases p esen in a mix u e is based on he
p inciple ha om he measu ed di ac ion in ensi ies he amoun o he c ys alline phases in he
mix u e can be modelled. In quan i a i e Rie eld analysis we assume ha he pa e n con ains only
c ys alline phases, whose concen a ion is e ined. Adding o he sample a known weigh o a
s anda d, he assump ion is checked. In he case ha he weigh o he s anda d is highe han
expec ed, he pe cen age o he c ys alline phases is adjus ed, wi h he addi ion o an amo phous
phase. To no e, he amo phous con en is gi en by di e ence, and no u he in o ma ion on i s
homogenei y o na u e is ob ained.
2.8 X-RAY FLUORESCENCE (XRF) ANALYSIS
2.8.1 XRF spec oscopy: con en ional sou ce
X- ay luo escence spec oscopy (XRF) is a quan i a i e analy ical echnique ha is used o de e mine
he elemen al composi ion o a ma e ial. XRF is based on he p ope y o a oms o emi X adia ion
cha ac e is ic o he elemen when hey a e exci ed by an X- ay beam. Fluo escence is induced by a
beam o p ima y elec omagne ic adia ion wi h ene gy o he o de o ens o keV. I is a mul i-
elemen al expe imen al echnique, ha is, i allows he simul aneous de ec ion o mos o he elemen s
p esen in he sample unde in es iga ion (majo , mino and ace elemen s).
In his wo k, he elemen al composi ion o all he g ain sizes o he conside ed W E plan s was
analysed by XRF. The BA we e c ushed and g ound wi h an aga e ball mill un il a ine homogeneous
powde wi h g ain size < 0.063 mm was ob ained. Table s o conduc ing XRF analyses we e p epa ed
using 3 g ams o BA g ound wi h 7 g ams o bo ic acid powde . The able s we e analysed a
Dipa imen o di Scienze Biologiche, Geologiche ed Ambien ali (Uni e si à di Bologna) wi h a
WDXRF Axios PanAly ical spec ome e , equipped wi h a Rh ube wo king a 4 kW. The analyses
we e pe o med on bo h majo elemen s (exp essed g/100g) and ace elemen s (exp essed in g/Kg).
30
2.8.2 µ - XRF spec oscopy: synch o on adia ion
XRF done wi h con en ional me hods gi es a bulk composi ion, a e age o he powde ed able . The
in ensi y and ocussing which can be ob ained om a con en ional X- ay sou ce a e no su icien o
pe o m an analysis a he local scale. This can be o e come when synch o on adia ion is used.
Synch o on adia ion is an elec omagne ic adia ion p oduced when a cha ge pa icle o mass m
(elec on o posi on) accele a ed o ela i is ic eloci y is being de lec ed in a magne ic ield. When
he speed o he cha ged pa icle inc eases o ela i is ic alues ( ≈ c) a adia ion is gene a ed wi h
se e al speci ic cha ac e is ics: 1) i is s ongly pola ised; 2) i has a e y low di e gence; 3) i
possesses a la ge and con inuous ange o ene gies (i ’s whi e), so scien is s can pick wha e e
wa eleng h hey need o hei expe imen s, as in a ed ligh , ul a iole o X- ays (so o ha d); 4)
i is e y in ense, se e al o de s o magni ude g ea e han con en ional X- ay ubes.
Using synch o on adia ion o exci e he analysed a ea o luo escence analysis we ha e a e y
in ense and ocussed beam, so ha a eas as small as 50x50 µm2 can be analysed.
Figu e 2.8.2.1 Scheme o a synch o on. Legend: 1) Linac; 2) Boos e ; 3) S o age ing; 4) Beamline;
5) F on end; 6) Op ics hu ch; 7) Expe imen al hu ch; 8) Con ol cabin; 9) RF ca i ies.
(www.diamond.ac.uk)
In his wo k synch o on adia ion was used o make µ - XRF maps and, as desc ibed in he ollowing
chap e , XANES analyses, a he XRF beamline a Ele a Sinc o one T ies e (ETS) (Figu e 2.8.2.1).
31
Figu e 2.8.2.2 (a) Pho og aph o he IAEAXspe ins umen ins alled a he XRF beamline o Ele a
Sinc o one T ies e (# Iain Da by/IAEA). (b) Se en-axis mo o ised manipula o . (A wo k cou esy o Hube
Di ak ions echnik GmbH & Co. KG.) (c) Mo emen ange o The a/2The a axes depic ed in a ho izon al
c oss-sec ional iew o he IAEA ends a ion (Ka ydas e al., 2018).
In his wo k, he expe imen has been conduc ed using bo h HE mul ilaye o he collec ion o µ-
XRF maps, wi h s anda d 45°/45° geome y o luo escence mode measu emen s, using an XFlash
5030 SDD de ec o (B uke , Be lin, Ge many). The la su ace o he BA sample embed in epoxy
esin has been moun ed on a Te lon sample holde , wi h also e e ence me al oils moun ed on he
side (pe pendicula ly) o he ene gy calib a ion o he monoch oma o (in ansmission mode, using
an Hamama su Si-pho odiode S3590-09, 10x10 mm2, 300µm hickness). This se up was necessa y o
secu e he sample and o ha e a sys em compa ible wi h he wo king condi ions o he Ul a High
Vacuum Chambe (UHVC, 10-7 mba ) a ailable a he XRF beamline. µ-XRF maps we e collec ed
wi h an inciden beam ene gy o 14 keV and a beam size a he exi sli s o 50x50 µm2 (H*V). Highe
o de ha monics con amina ions we e supp essed by a pai o pa allel plane mi o s in e cep ing he
beam in g azing incidence (Figu e 2.8.2.2).
2.9 X-RAY ABSORPTION SPECTROSCOPY (XAS)
Abso p ion spec oscopy e e s o a numbe o expe imen al echniques used o acqui e in o ma ion
on he elec onic, s uc u al and magne ic p ope ies o he ma e . They a e based on he s udy o he
a ia ions o he linea abso p ion coe icien as a unc ion o he ene gy o he inciden pho ons. In
he case in which X- ay a e used as adia ion we a e alking abou X- ay Abso p ion Spec oscopy
(XAS). The linea a enua ion coe icien depends bo h on he sca e ing phenomena (elas ic o
inelas ic), and on he pho oelec ic abso p ion. In he ange o ene gies used o pe o m XAS (1-40
KeV) he componen due o he abso p ion clea ly domina es ha caused by di usion; he e o e, he
32
a enua ion coe icien can be app oxima ed as he coe icien o pho oelec ic abso p ion. On la ge
ene gy anges, abso p ion coe icien a ies acco ding o a law epo ed below:
𝜇 ≈ 𝑑𝑍4
𝑚𝐸3
whe e Z is he a omic numbe o he a ge a om, m i s mass, d he densi y o he sample and E he
ene gy o he pho on.
Figu e 2.8.1 G aph o he abso p ion coe icien o Pb in unc ion o he ene gy o he pho ons o he beam
(www.physics.nis .go )
In Figu e 2.8.1 i appea s ha abso bance shows some discon inui y in co espondence o pa icula
ene gies. These a e due o pho oelec ic abso p ion by quan ized ene gy alues. When he ene gy o
he beam is su icien o ex ac he elec on in a gi en ene gy le el a la ge numbe o pho ons is
abso bed by he sample, d ama ically dec easing he numbe o ansmi ed pa icles. This
consequen ly causes he appea ance, in he icini y o ha pa icula ene gy, o a discon inui y in he
abso p ion spec um. By s udying hese seemingly i egula s uc u es and hei ene gy dis ibu ions,
i is possible o ob ain ha o he inne mos elec onic shells o he a ious chemical elemen s.
Mo eo e , sinusoidal oscilla ions o he abso p ion coe icien occu a ound he alue assumed in he
peak, ha is, o he p esence o a ine s uc u e.

33
When a XAS spec um is analysed, is possible o ob ain di e en in o ma ion depending on he
conside ed ange o ene gy; o his eason, is con enien o di ide he spec um in o h ee dis inc
egions:
• P e-edge egion: limi ed ene gy ange o a ew eV be o e he abso p ion edge. I ’s possible o
de ec he p esence o weak discon inui ies (p e-edge peaks) due o ansi ion o co e elec ons
o o he bound s a es.
• X- ay Abso p ion Nea Edge S uc u e (XANES): i is he pa o he spec um which ex ends
om 0 o 50 eV abo e he abso p ion edge; he combined s udy o XANES and p e-edge
p o ides in o ma ion on geome ic and elec onic local con igu a ion. In o he wo ds i is
pa icula ly use ul o ob ain in o ma ion on he s a e o chemical bond be ween di e en a oms
o he sample and is s ongly a ec ed by he oxida ion s a e o he abso be a om. This was
he echnique used in his wo k.
• Ex ended X- ay Abso p ion Fine S uc u e (EXAFS): de ines he egion o he spec um
be ween 100 and 1000 eV beyond he abso p ion edge. F om EXAFS analysis is possible o
de e mine he geome ic s uc u e o he sample in he immedia e icini y o he abso be a om
(up o 10 Å).
Figu e 2.8.2 Example o an XAS spec um o Fe and i s componen s (www.commons.wikimedia.o g)
Since XANES is a much la ge signal han EXAFS, XANES spec a can be collec ed e en in sample
con aining lowe concen a ions o he a ge elemen . The in e p e a ion o XANES spec a is
complica ed as he e is no a simple analy ic o physical desc ip ion o XANES. Howe e , he spec a
can be in e p e ed by compa ison wi h e e ence samples, and, as he edge posi ion and shape is
34
sensi i e o o mal alence s a e, ligand ype, and coo dina ion en i onmen , he XANES spec a can
be used as a inge p in o iden i y phases. An impo an and common applica ion o XANES is o
use he shi o he edge posi ion o de e mine he alence s a e; he heigh s and posi ions o p e-edge
peaks can also be eliably used o empi ically de e mine oxida ion s a es and coo dina ion chemis y
(Figu e 2.8.2). A majo ad an age in XANES is o be elemen sensi i e, and o de ec an elemen e en
in ppm concen a ions. Also, e en when a gi en elemen unde he beam is ep esen ed by mo e han
one phase, a decon olu ion can be done o assess he di e en con ibu ions unde he beam o he
phases whe e he elemen is p esen .
In his wo k, some PTE (Cu, C , Zn, Pb, Ni, and Co) we e analysed by XANES in o de o in es iga e
hei oxida ion s a e and he mine alogical en i onmen in which hey we e hos ed. XANES
measu emen s we e conduc ed a he Ele a XRF beamline. The expe imen has been conduc ed
using Si111 monoch oma o s, wi h s anda d 45°/45° geome y o luo escence mode measu emen s,
using an X-Flash 5030 SDD de ec o (B uke , Be lin, Ge many). All spec a we e collec ed using 5
seconds pe s ep and a a iable ene gy s ep as a unc ion o he ene gy: La ge s ep (5 eV) in he i s
200 eV o he spec um, smalle s ep (0.2 eV) in he nea -edge egion and a k-cons an s ep o 0.05
Å-1 u he abo e he abso p ion edge. Mul iple spec a ha e been collec ed and me ged in o de o
inc ease he signal o noise a io. The oxida ion s a e will be de e mined using leas -squa es Linea
Combina ion Fi ing (LCF) based on e e ence spec a collec ed on compounds o known oxida ion
s a e. Backg ound emo al, no malisa ion o XANES spec a and LCF analyses will be pe o med
using he A hena so wa e package.
2.10 LEACHING TEST
The leaching es is a special ype o chemical ex ac ion. The ma e ial (soil, was e o sludge)
unde goes a chemical a ack wi h a eagen (liquid) in o de o assess, h ough he analysis o he
elua es, he elemen s eleased om he solid sample. The es makes i possible o es ima e he
po en ial long- e m elease o he compounds con ained in soils o was es, pa icula ly hose ha
could cons i u e po en ial pollu ion o he en i onmen al ma ices.
In his wo k, leaching es s and analysis o he leacha es we e pe o med ollowing he UNI EN
12457-2:2004 “Was e Cha ac e iza ion - Leaching - Compliance es o g anula was e and
sludge leaching - Pa 2: Single-s age es wi h a liquid/solid a io o 10 l/kg o ma e ials wi h
pa icle sizes less han 4 mm (wi h o wi hou size educ ion)”, which in his case has been adap ed
o BA assessmen . This is a single-s age es called “ba ch leaching me hod”, whe e a gi en olume
o sample is placed in a olume o leacha e solu ion o a gi en pe iod o ime. This me hod equi es
35
some ype o agi a ion o ensu e cons an con ac be ween he sample and leacha e. A he end o he
leaching pe iod, he liquid is emo ed and analysed.
Following guidelines which indica e a liquid o solid a io o 10 o 1 (L/S = 10:1), he es was
conduc ed in 50ml alcons in o which 3g o BA and 30ml o ul apu e wa e (Milli-Q ® 18.2 MΩ.cm
a 25 °C and TOC < 5 ppb). The es was ca ied ou on he pa icle size classes below 4mm om all
he i e W E plan s examined. Th ee eplica es we e p epa ed o each g ain size class o g ea e
accu acy o he da a and a “blank” sample con aining only 30ml o ul apu e wa e . The en i e
expe imen al p ocedu e can be summa ised as ollows:
● he samples we e placed in o a o shake o 24h a 30 pm;
● a e 24h, each sample was cen i uged a 3600 pm o 10 minu es in o de o sepa a e he
elua e om he solid ac ion;
● he samples we e il e ed and he elua es we e collec ed; pH, empe a u e and elec ical
conduc i i y we e no ed;
● he samples we e acidi ied wi h 3 d ops o ni ic acid
The leacha es we e dilu ed 1:2 and hen 1:100 and we e analysed by a omic abso p ion, ion
ch oma og aph, and ICP-MS (analy ical echniques ha will be explained in de ail la e ) in o de o
e alua e majo elemen s, ions, and mino o ace elemen s.
2.11 SEQUENTIAL EXTRACTION PROCEDURE (SEP)
The SEP is a p ocedu e whe e he sample unde goes a se ies o chemical e ching o dissol e he solid
phases, in esponse o hei chemical beha iou . Wi h his p ocedu e, we may de ec mino phases
which om he X- ay di ac ion o he o iginal sample could be o e looked.
The S anda ds, Measu emen s and Tes ing ( o me ly BCR) p og am has p oposed a h ee-s ep
sequen ial ex ac ion p ocedu e o he analysis o sedimen con aminan s (Rau e e al., 1999). The
p ocedu e consis s o h ee s eps in which he sample o be analysed is a acked sequen ially by
di e en eagen s and he elua es a e analysed o assess which elemen s and in wha amoun s ha e
passed in o solu ion.
Se e al s udies in he li e a u e (Ab amo e al., 2018; Alam e al., 2019; Habe l & Schus e , 2019;
Pé ez-Ma ínez e al., 2019; Tong e al., 2020; Akyniemi e al., 2020) apply and modi y BCR 176 o
he s udy o BA and FA. In his wo k, a sequen ial ex ac ion p ocedu e was de eloped based on he
ma e ial’s esponse o di e en chemical a acks which will be desc ibed below.
SEP was conduc ed on he Piacenza BA (sampled in 2019) and he Pa ma BA (sampled in June 2021).
Speci ically, o Piacenza ma e ial om 0.2 - 0.3mm g ain size was analysed, while o Pa ma 2021
h ee pa icle size classes (0.063-0.2, 0.3 - 0.5, 2 - 4 mm) and a bulk made om he pa icle size
36
classes < 4mm we e analysed. Fo each sample, 30g o ma e ial was aken and qua e ed o ob ain
samples o 1g each.
The inal p ocedu e consis s o 5 s eps desc ibed below, each o hem p omo ing dissolu ion o a
gi en po ion o he ma e ial (Figu e 2.11.1):
● STEP 1 (wa e -soluble ac ion): he i s s ep aimed o emo ing wa e -soluble phases, such
as hyd a ed phases (e ingi e). In cen i uge- ubes (50ml), 1g o BA and 40 ml o ul a-pu e
wa e we e added. The samples we e placed in an oscilla ing shake a 30 pm o 16h
(o e nigh ) a oom empe a u e. Then, he solid ac ion was sepa a ed om he liquid
ac ion by cen i uga ion a 3000g o 20min (o un il all suspended pa icles we e
p ecipi a ed). Th ough a il e appa a us wi h a acuum pump, he elua e ob ained was il e ed,
collec ed and s o ed wi h 3 d ops o HNO3 a a empe a u e o 4°C.
● STEP 2 (ca bona e ac ion): he second s ep is aimed o emo ing ca bona e ac ion, such
as calci e and a e i e. In he cen i uge- ube (50ml), 40ml o 5mol/l ace ic acid was added o
each solid esidue om he p e ious s ep. The samples we e placed in an oscilla ing shake a
30 pm o 16h (o e nigh ) a oom empe a u e. Then, he solid ac ion was sepa a ed om
he liquid ac ion by cen i uga ion a 3000g o 20min (o un il all suspended pa icles we e
p ecipi a ed). Th ough a il e appa a us wi h a acuum pump, he elua e ob ained was il e ed,
collec ed and s o ed a 4°C. Solid esidues a e washed wi h ul apu e wa e h ee imes in a
cen i uge and hen p oceed o he nex s ep o a e s o ed o conduc chemical-mine alogical
analysis.
● STEP 3 ( educible ac ion): he hi d s ep is aimed o emo ing educible ac ions, such as
Fe – Mn oxyhyd oxides. The esidues om he p e ious ex ac ion s ep a e added o 40 ml o
hyd oxylammonium chlo ide 0.5mol/l. The samples a e placed in an oscilla ing shake a
30 pm o 16h (o e nigh ) a oom empe a u e. Then, he solid ac ion is sepa a ed om he
liquid ac ion by cen i uga ion a 3000g o 20min (o un il all suspended pa icles a e
p ecipi a ed). Th ough a il e appa a us wi h a acuum pump, he elua e ob ained is il e ed,
collec ed and s o ed a 4°C. The solid esidues a e washed wi h ul apu e wa e h ee imes in
a cen i uge and hen p oceed o he nex s ep o a e s o ed o conduc chemical-mine alogical
analysis.
● STEP4 (oxidable ac ion): his s ep is aimed o emo ing oxidable ac ion, such as o ganic
ma e and sulphide. solid esidues om he hi d s ep a e ans e ed in o glassy beake s wi h
10 ml o hyd ogen pe oxide. beake s a e co e ed wi h a glass wa ch and diges ed a oom
empe a u e o 1h wi h occasional manual shaking. Diges ion con inues o 1h a 85°C in a
he mos a ic ba h, hen educe he olume o less 3ml by u he hea ing o he unco e ed
43
he Eu opean Council Regula ion 2017/997 conce ns he hea y me als glass and mine al-bea ing
phases, hei iden i ica ion and cha ac e iza ion, and hei wea he ing beha io (EU 2017/997).
I is es ablished ha he smalle po ion o he bo om ashes is he mo e pollu ed (Alam e al., 2020;
Wiles, 1996). This was sys ema ically e i ied in a ecen in es iga ion ha so ed he BA in a ange
o di e en g ain sizes. BA so ing p oduces new was e wi h he u he disad an age ha smalle
sized g ains p o ide a la ge eac ion su ace and, possibly, highe leaching o hea y me als al eady
p esen a signi ican concen a ions (Alam e al., 2020; Alam e al., 2019a; Ca iglia e al., 2019;
Logino a e al., 2019; Šyc e al., 2020). Reco e y o he smalle ac ion o he BA was p oposed in
ega d o py oxene glass ce amics by hea ing a a high empe a u e (Bou salas e al., 2014). Howe e ,
cha ac e iza ion h ough di e en sizes o he BA is equi ed o plan any p ocess o eco e y.
P e ious in es iga ions ocused on he cha ac e iza ion o he mine al phases (Alam, e al., 2019a;
Bayuseno & Schmahl, 2010)o he analysis o he po ions sie ed om bo om ashes (Ca iglia e al.,
2019; Šyc e al., 2020). A sys ema ic in es iga ion ega ding mine alogy, composi ion, and g ain size,
o cons ain he hos o he po en ially oxic elemen s (PTE) is s ill lacking. I is no clea whe he
he PTE a e always concen a ed in small g ain sizes o whe he hei p esence p ima ily depends on
he was e inpu o he ype o plan (Hyks & As up, 2009).
This s udy compa es he a e age mine alogical and chemical composi ion o each ac ion di ided
by g ain size, using esul s om he li e a u e and new da a om he was e- o-ene gy plan (W E)
loca ed in Pa ma. X- ay di ac ion, chemical analysis o majo and mino elemen s, and op ical and
elec on mic oscopy, oge he wi h mic op obe analysis obse a ions, a e used o cla i y he ends
ollowed by PTE in e ms o g ain size and BA mine alogy. The aim o his s udy is o de e mine how
g ain size a ec s he dis ibu ion o he di e en elemen s and any possible euse and ecycling
implica ion
2. Ma e ials and Me hods
2.1 The Bo om ash sampling and sie ing
Municipal solid was e incine a ion (MSWI) bo om ash was collec ed om he W E plan o Pa ma
(no he n I aly), which is loca ed in he i s subu bs o he ci y in he PAIP (Polo Ambien ale
In eg a o pe la ges ione dei i iu i di Pa ma—En i onmen al In eg a ed A ea o was e managemen ).
Designed and buil by I en G oup, he plan has been ope a ing since 2014, co e ing abou 150.000
ons/yea o ma e ial in 2019. The main eeds ock was e includes a d y ac ion selec ed om
undi e en ia ed municipal solid was es (70.000 /yea ); special un ecycled was es (18.000 /yea );
discha ges om was e eco e y and disposal (15.300 /yea ); sani a y was es (3.500 /yea ); ceme e y
was es (200 /yea ); indus ial, handic a , and comme cial p ocesses was es (3.000 /yea ); and d ied

44
sewage sludge (20.000 /yea ). The plan p oduces abou 32.000 /yea o BA, as well as slag and ly
ash (abou 20% o he ashes).
Fi e samples, each weighing abou 600 g, we e aken, blending a la ge amoun o ma e ial om
di e en poin s o he bo om ash pile loca ed inside he plan on i e di e en days (1–5 Decembe
2018) o conside he a iabili y o he ma e ial. The indi idual samples we e mixed; he o al sample
o abou 3 kg o esh BA was d ied in he o en a 50° C o 24 h and sie ed in o de o assess he
g ain size dis ibu ion. The openings s anda ds used we e chosen acco ding o Eu opean s anda ds
o agg ega e EN 933–2 (En e I aliano di Uni icazione, 2020), and he g ain size used o u he
in es iga ion was di ided in o nine classes (<0.063, 0.2, 0.3, 0.5, 1, 2, 4, 8, >16). The cumula i e
g ain size dis ibu ion is shown in Figu e 3.1.1.1.
Figu e 3.1.1.1 Cumula i e pa icle size dis ibu ion and compa ison wi h he Fulle cu e and wi h
li e a u e da a (Syc e al., 2018; Funa i e al., 2015; Ca iglia e al., 2019; del Valle-Ze meno e al, 2017;
Fulle e al., 1907).
2.2 X- ay Fluo escence Spec ome y (XRF)
The bulk composi ion was measu ed o each g anulome ic class by means o X- ay luo escence
spec ome y (XRF). Abou h ee g ams o he d ied and milled ma e ial was used. Be o e analysis,
each sample was i s p essed in a bo ic acid binde o ob ain a hin-laye p essed powde pelle (37
45
mm in diame e ). A sequen ial wa eleng h dispe si e X- ay luo escence (XRF) spec ome e (Axios-
Panaly ical), equipped wi h a 4 kW Rh ube and Supe Q 3.0 so wa e, was used. To al loss on igni ion
(LOI) was g a ime ically es ima ed a e o e nigh hea ing a 950° C. The analy ical esul s in Table
3.1.1.1. a e p o ided wi h measu ed s. ce i ied alues o he ce i ied e e ence ma e ial (CRM)
BCR-CRM176R. The es ima ed p ecision o elemen al de e mina ions is be e han 5% o all
elemen s, excep hose occu ing a concen a ions lowe han 10 mg/kg, o which he p ecision is
compa ably wo se (10–15%).
2.3 X- ay powde di ac ion (XRPD) phase analysis
X-Ray Di ac ion (XRD) was pe o med on each o he sie ed po ion, and on ew mm-sized g ains
chosen in unc ion o he op ical appea ance. A B uke D2 Phase powde di ac ome e wi h Cu Kα
(λ=1.54178 Å) adia ion, 30 kV and 10 mA, Ni il e ed, 2θ be ween 5 and 70°, wi h s eps o 0.02°
and a sampling ime o 1 s was used. The di ac ome e ac s wi h a θ-θ ocalizing geome y and akes
ad an age o a solid-s a e de ec o . A sample o a ion o 30 pm was applied o minimize c ys al
p e e en ial o ien a ion e ec s. The di ac ion pa e ns we e iden i ied using he B uke so wa e
EVA and he C ys allog aphy Open Da abase (COD). The complexi y gi en by he numbe o
mine alogical phases hinde ed a quan i ica ion h ough Rie eld e inemen o all he phases p esen .
The majo c ys alline phases, ound in all samples, we e quan i ied using he GSAS 2 so wa e
package (Toby & Von D eele, 2013). The amo phous con en was es ima ed by Rie eld analysis
(Rie eld, 1993) using high pu i y Al2O3 co undum (10 w %) as an in e nal s anda d. The e ined
phases and hei abundance a e lis ed in Table 3.1.1.2.
2.4 Op ical and SEM-EDS mic oscopy
Twel e la ge agmen s (>8 mm) we e embedded in epoxy esin and cu longi udinally o ob ain hin
and polished sec ions o he analysis. The embedded g ains we e selec ed o a oid unbu n and
e ac o y ma e ials, which we e ins ead pa o he powde analyzed by XRD and XRF. The sec ions
we e i s obse ed by a pola ized s e eomic oscope (BX51, OLYMPUS), and hen wi h a Scanning
Elec on Mic oscope coupled wi h Ene gy Dispe si e Sys em (SEM-EDS) JSM IT300LV Jeol 6400
equipped wi h an Ox o d EDS mic op obe. Mic op obe analysis was pe o med wi h ope a ing
condi ions 20 o 25 kV and 1.2 mA cu en , ~1µm beam diame e and 75 s coun ing ime. Analyses
a 25 kV we e pe o med in o de o enhance he con ibu ion o he highe ene gy peaks in me als
and hea y me als.
2.5 S a is ical analysis
46
A desc ip i e s a is ic is applied o selec ed chemical and mine alogical esul s based on g ain size as
a disc iminan a iable and used o compa a i e analysis wi h wo sui able wo ks ecen ly ca ied
ou by Ca iglia e al. (2019) and Logino a e al. (2019). The co ela ion was in es iga ed by
calcula ing he linea eg ession ( , Pea son) and Spea man’s ank p o de co ela ion coe icien .
S a is ical analysis o da a dis ibu ions was pe o med using SPSS so wa e (IBM co po a ion, 2017)
and epo ed in APPENDIX I.
3. Resul s
3.1 G ain size dis ibu ion
In Figu e 3.1.1.1, he g anulome ic cu e o samples is shown and compa ed wi h ha o o he
incine a o s wi h simila echnology and condi ions as epo ed by Ca iglia e al. (2019), Funa i e
al., (2015), Šyc e al., (2018) and del Valle-Ze meño e al. (2017). The Fulle cu e, which ep esen s
he op imal agg ega e dis ibu ion cu e in e ms o densi y and s eng h, is also plo ed (Fulle &
Thompson, 1907). Some o he di e ence may come om he sampling p ocedu e: he cu es a y
in dependence on he po ion o he ashes pile which is sampled, o e es ima ing he la ge size in he
lowe po ion (A. F. Gual ie i, 2000), bu o all he g anulome ic plo s, he ac ion lowe han 4 mm
accoun s o abou 55 w %.
In pa icula , he cumula i e pa icle size dis ibu ion o Pa ma shows ha he mos o BA (abou
60%) lies in he ange o 2-9 mm ( ange o coa se sand and g a el) while a 20% o he o al weigh
has a g ain size <2 mm and ano he 20% is he ac ion >9 mm. A di e ence exis s in he po ion
below 1 mm, which is jus 6 w % in Pa ma and Funa i e al. 2015, whe eas i is up o 20 w % in o he s
(Logino a e al. 2019). Compa ing he shape o he Fulle cu e o ou samples, we ha e a lowe
pe cen age - abou 5-10 w % -o ine ma e ial (below he 3 mm).
3.2 Chemical analysis o MSWI bo om ash
The bulk chemical composi ion wi h g ain size is epo ed in Table 3.1.1.1. Pea son’s - alue and
he Spea man ank p o es co ela ion be ween elemen s and wi h g ain size is epo ed in
APPENDIX I.
In he Pa ma bo om ashes, Si is en iched in he la ge g ains and Ca in he smalle ones. The e a e
se e al elemen s ha a e posi i ely co ela ed wi h Si o wi h Ca. The posi i e end wi h Si is
ollowed by Rb and Z , and, among majo elemen s, by Al, Fe, K, and Mg, when only he po ions
smalle han 2 mm a e conside ed. In his case, he co ela ion is s ong (R2 > 0.9). Se e al o he
elemen s a e posi i ely co ela ed wi h Ca, and nega i ely wi h g ain size: hey a e S, Cl, Zn, Cu, Ba,
Pb, As, Sn, Ti, and S . Few elemen s, C , Ni, V, and Ce, do no seem o be ela ed o Si o Ca.
47
majo elemen s
(g/100g)
g ain size (mm)
>16
8-16
4-8
2-4
1-2
0.5-1
0.3-0.5
0.2-0.3
0.063-0.2
<0.063
SiO2
46.23
45.82
38.95
37.75
35.91
31.72
29.20
25.71
24.85
23.71
CaO
21.60
21.78
24.79
24.66
24.63
26.67
28.41
29.67
30.12
30.05
Al2O3
8.59
8.26
8.92
10.39
10.05
9.63
8.96
8.27
8.46
8.27
MgO
3.71
3.95
3.64
4.33
4.42
3.91
3.59
3.26
3.15
3.23
Fe2O3
3.04
3.01
3.60
3.63
4.05
3.74
3.48
2.64
2.49
2.21
Na2O
3.92
3.69
2.78
2.49
2.36
2.20
2.18
2.14
2.26
2.20
P2O5
1.52
1.30
1.59
2.22
2.11
2.10
2.19
2.00
1.91
1.82
K2O
1.21
1.29
1.26
1.36
1.45
1.35
1.29
1.23
1.19
1.11
TiO2
0.69
0.64
0.78
0.86
0.90
0.97
0.92
0.90
0.90
0.90
MnO
0.09
0.08
0.11
0.09
0.10
0.10
0.10
0.09
0.09
0.10
LOI
9.40
10.19
13.60
12.22
14.02
17.62
19.69
24.08
24.58
26.40
Mino and ace elemen s
(mg/Kg)
S
8070
7780
9600
9500
10900
12840
14780
16910
17740
16420
Cl
5430
5430
7420
8050
8236
9780
10120
10530
10960
11600
Cu
1261
1413
1104
1669
1335
1640
1885
1664
1637
2041
Zn
1380
4400
1660
3630
3830
4270
5750
5940
6830
8740
Ba
955
907
1098
1684
1461
1681
1618
1631
1529
1879
Pb
1354
409
312
545
676
800
802
913
981
1172
C
880
629
573
434
651
644
697
592
621
627
S
429
378
436
681
499
485
517
571
568
572
Z
256
212
186
207
196
173
169
155
156
143
Ni
119
183
140
135
174
144
179
132
134
160
Co
27
27
32
25
62
51
57
44
44
43
V
61
69
73
84
84
90
79
78
78
79
As
54
26
41
36
47
52
56
59
59
74
Ce
37
44
41
46
47
48
36
29
38
51
Sn
19
17
19
44
36
53
43
49
58
91
Rb
32
34
31
30
32
30
27
27
25
24
La
18
35
13
8
25
30
21
6
14
16
Y
14
16
16
17
19
15
14
12
12
11
Nd
18
19
10
10
22
18
20
2
19
5
Mo
15
10
15
11
17
14
13
15
14
14
Ga
14
13
12
13
13
13
14
14
13
14
Nb
11
10
11
12
12
11
10
10
11
10
Sc
<3
6
10
15
10
6
13
14
18
14
Th
13
7
6
5
7
7
7
8
9
9
H
<3
7
6
4
3
<3
<3
<3
<3
<3
U
<3
3
<3
<3
<3
<3
<3
<3
<3
<3
Table 3.1.1.1 X- ay luo escence spec ome y (XRF) analysis o majo , mino , and ace elemen s o
he bo om ashes (BA) samples o Pa ma was e- o-ene gy (W E) plan di ided by g ain size. Elemen s
a e in mg/kg, bu majo elemen s a e exp essed as g/100 g o hei oxides and loss on igni ion (LOI)
alues in %. The measu ed s. ce i ied concen a ions o he ce i ied e e ence ma e ial (CRM), BCR-
CRM176R, is p o ided wi h he same uni o measu e (n.a. is no a ailable).
Thus, we ind a Si- end, which is ollowed by li hophyle elemen s, i.e., hose ha ing an a ini y o
Si, inco po a ed in silica es, and a Ca- end, o elemen s wi h an a ini y o ca bona es and sul a es
(Ca, Ba, Zn, and Pb), sul ides (Sn and As), oxides (Ti), o possibly o he unbu n o ganics (LOI, Cl,
and S).
Si-and Ca- ends a e also p esen in o he pape s whe e he composi ion was de e mined wi h g ain
size. The di e ences wi h hese obse a ions a e ha Logino a e al. (2019) showed a s ong
co ela ion wi h Ca and S o Ni and C , and Ca iglia e al. (2019) showed ha Ni, bu no Cu,
ollows he Ca- end (Table S1). Mo eo e , he posi i e co ela ion wi h Si o Fe, Mg, K, and Al in
he smalle g ains is no con i med; in Logino a e al. (2019), Fe has a nega i e co ela ion wi h Si.
Wi hin he abo e co ela ions, he e is a s ong di e encein he ac ual composi ional alues (Figu e
48
3.1.1.2). Si s. Ca ch anged wi h a simila slope in his wo k and in ha o Logino a e al. (2019), bu
shi ed o lowe Ca con en in he wo k o Logino a e al. (2019); simila ends a e ound by Ca iglia
e al. (2019) bu o he h ee ine g ain sizes, which show highe Ca con en han expec ed ollowing
he end o Pa ma
(Figu e 3.1.1.2 a). F om he analyses o smalle g ains, i appea s ha Ca om di e en plan s
changes simila ly wi h S, wi h an appa en de ia ion om he main end (Figu e 3.1.1.2 b). Pb and
Zn ollow a simila end in he wo k o Logino a e al. (2019) and in his wo k, bu hey ollow a
di e en end in he wo k o Ca iglia e al. (2019) (Figu e 3.1.1.2 c). No co ela ion be ween S and
C is ound in any s udies. I is likely ha hese di e ences in chemical composi ion may come om
he was e inpu and di e en bu ning p ocesses o he W E plan s, despi e he ac ha a co ela ion
be ween inal composi ion and was e inpu may be e y di icul o p edic wi h cu en knowledge.
Figu e 3.1.1.2 Compa ison be ween a) Si s Ca, b) S s Ca, c) Pb s Zn, alues o his wo k (g een
bulle ) da a om Logino a e al. 2019 ( ed squa es) and Ca iglia e al. 2019 (da k squa es).

49
3.3 XRPD and Rie eld analysis
All o he X- ay powde di ac ions show he e ogeneous assembly o se e al c ys alline phases,
oge he wi h signi ican glass con en (Figu e 3.1.1.3). To iden i y he mine alogical phases, in
addi ion o he s anda d X- ay di ac ion pa e n made on he di e en g ain-sized po ion, selec ed
on he basis o hei aes he ic appea ance, hey a e aken om he o al sample and discussed. The
main goal o his p ocedu e is he cha ac e iza ion o speci ic phases ha a e ha dly ecognizable due
o hei small quan i ies inside he sample. Mic oscopic images o he isola ed clas s and hei
iden i ica ion wi h XRD analysis a e epo ed in APPENDIX II. Thei composi ion is e y
he e ogeneous and is ep esen ed by small pieces o g een, b own, o anspa en glass (poin 3); whi e
spongy g anules o hyd oxyapa i e o bone esidues (poin 5); pieces o non-combus ed piece o me al
(poin 4); and g ay agg ega es wi h ed o da k a eas, which a e he ypical p oduc o he bu ning
p ocesses. The mine al phases ound in hese g ey clas esemble hose no ed in he bulk sample and
mos o he po ions a e sie ing.
Figu e 3.1.1.3. XRD pa e ns made on di e en g ain sizes. Alumina (Al2O3) s anda d is used.
50
Phase iden i ica ion was biased by he numbe o o e lapping peaks, which concealed he peaks o he mino
phases. Mo eo e , isomo phic subs i u ions in plagioclase, gehleni e, phospha es, and sul a es gi e ise o a
shi in peak posi ions, again hinde ing co ec iden i ica ion. In Table 3.1.1.2, quan i a i e Rie eld analysis
was conduc ed on he ew phases ha could be uni ocally iden i ied. The esul s o he Rie eld e inemen
a e gi en in weigh pe cen no malized o 100%, including he amo phous ac ion es ima ed wi h he aid o
he co undum in e nal s anda d.
As shown in Table 3.1.1.2, he amo phous phases a e he main cons i uen s in BA. The amo phous phase is
highe in he la ge g ain sized po ions, be ween 75 and 70 w %, andlowe in he smalle ones, be ween 60
and 65%. The esidual glass likely explains he highe amo phous phase con en in he la ge g ains. C ys alline
silica es (qua z and melili es) a e p esen in highe pe cen age in la ge g ains, whe eas ca bona es, calci e,
and a e i e occu mo e in smalle sized ac ions. As expec ed, his ag ees wi h he chemical analy ical esul s,
bu as discussed below, mos Ca and Si a e p esen wi hin he amo phous phases. E ingi e is concen a ed
mo e in he ine ac ions, whe eas less abundan hyd ocalumi e,s ä lingi e, and i on oxides appea o be
un ela ed o g ain size. Calci e is he only c ys alline phase p esen wi h a concen a ion highe han 10%. I s
concen a ion in lowe g ain sized po ion is likely ela ed o he small size o c ys als, which a e o med du ing
he ca bona ion p ocess in ai . Compa ed o o he in es iga ions, a di e ence in a mino con en o eldspa is
e iden (Bayuseno & Schmahl, 2010; Logino a e al., 2019; Wei e al., 2011a), whose place is pa ially aken
by Ca-Al-Si phases, such as e ingi e, s ä lingi e, and hyd ocalumi e. Mo eo e , syl i e, ano he commonly
ound phase, is missing he e. The amo phous phases he e a e mo e p esen han hose in he wo ks Bayuseno
and Schmahl (2010) and Alam e al. (2019a), who ound an amo phous o 33 and 36 w %, espec i ely, bu
hey a e simila o hose iden i ied by Ca iglia e al. (2019), i.e., abou 70%. An in e media e alue was ound
by Wei e al. (2011a) o abou 50%.
Phases
G ain Size (mm)
< 0.063
0.063-0.2
0.2-0.3
0.3-0.5
0.5-1
1-2
2-4
4-8
8-16
>16
Calci e
10
11
10
9
8
8
5
7
5
7
Qua z
3
4
2
6
3
5
6
6
4
5
S a lingi e
2
2
2
2
2
1
1
1
1
1
E ingi e
4
6
5
3
3
2
1
1
3
3
Hyd ocalumi e
3
4
4
4
3
3
3
3
3
2
Ano hi e
2
2
2
7
2
3
3
2
1
2
Va e i e
3
3
4
4
2
3
1
2
2
2
Gehleni e
2
3
3
2
2
2
2
2
2
2
Hema i e
1
1
1
1
3
1
< 1
< 1
< 1
< 1
Magne i e
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
C ys alline
30
36
33
36
28
27
23
24
20
25
Amo phous
70
64
67
64
72
73
77
76
80
75
Table 3.1.1.2 Rie eld e inemen quan i a i e phase analysis (w %) on di e en g ain size. The es ima ed
e o is ±1.
51
3.4 Bo om ash mo phology
3.4.1 Op ical obse a ion
Op ical obse a ion was done on ew g ains, chosen o di e en colou and lus e, om he po ion
la ge han 4mm. Simila g ains we e also analysed by XRD (APPENDIX II). The g ain colou a ies
wi h he c ys alline and amo phous phase con en , as e ealed by XRD. The ew whi ish g ains we e
made o hyd oxyapa i e, likely by he bu ning o ceme e y esiduals; g een o colou less glass come
om esidual glass, which did no eac du ing incine a ion. The ounded eddish-g ey g ains, which
a e mos abundan he e, in Chimenos e al., (1999,2003) and in Wei e al., (2011) a e mos made by
a he e ogeneous agg ega ion o esidual e ac o y ma e ial and me als coexis ing wi h c ys als and
amo phous (Figu e 3.1.1.4). The amo phous ac s as a ma ix ha binds he c ys alline and me allic
ac ions o he o iginal was e and he new- o med mine als. The o iginal was e g ains show ounded
edges, indica ing pa ial eabso p ion (Figu e 3.1.1.4 a), whe eas new o med c ys als a e o en
p esen as sha p needles wi hin he glass, like he wollas oni e c ys als in Figu e 3.1.1.4 b. Vesicles
and bubbles appea indica ing ha some degassing occu ed (Figu e 3.1.1.4 c and 3.1.1.4 g).
XRD and subsequen SEM-EDS analysis showed ha he g ey g ains ake hei colou o he
coexis ence o gehleni e and wollas oni e, mingled wi h me al, whe eas he ed po ions ake hei
colou om Fe oxides (Table 3.1.1.2 and APPENDIX III). Seconda y ca bona ion is p esen as an
ex e nal, ine g ey cohesi e ma e ial ha coa s he ounded clas s (Figu e 3.1.1.4 ).
3.4.2 SEM-EDS in es iga ion
SEM backsca e ed elec on images show almos in a iably c ys als wi hin an amo phous ma ix. The
p e ailing amo phous was in es iga ed in u he de ail. Abou 400 EDS poin analyses we e done on
di e en amo phous a eas, sampling i e polished sec ions sized abou 8-10 mm; in each i e a eas
we e examined, o a o al o 20 a eas. The poin analyses on he amo phous a e plo ed in he e na y
diag am SiO2-CaO-Al2O3 in Figu e 3.1.1.5, oge he wi h he bulk XRF composi ion o he 9
g anulome ic classes ( ed c osses).
The amo phous ma e ial is made o an ex eme he e ogeneous composi ion, coexis ing unmixed a
he sub-millime e scale e en wi hin he same g ain. This kind o mingling, well known in igneous
pe ology is ela ed o he c ys al s uc u e o silica- ich and silica-poo mel s, he e occu ing a he
mic oscale (Rankin, 1915). The composi ion o he amo phous wi hin each olume is homogeneous
(Figu e 3.1.1.4).
Op ically, his is appa en in he coexis ence o eddish and whi ish glasses. The chemical
composi ion o he glassy ma e ials is epo ed in he SiO2-CaO-Al2O3 e na y diag am. Mos
amo phous composi ions all nea o abo e he co ec ic lines, wi h a c owding on he e na y
52
minimum; his sugges s ha he amo phous glass o ms om mel a eu ec ic condi ions. Abou 80%
o he analyses alls wi hin he ield wi h co ne ed by pseudowollas oni e-gehleni e-la ni e. As shown
in Figu e 3.1.1.4 he a e age composi ion o he la ge g ains is Si- iche han almos all he analysed
glasses.
Figu e 3.1.1.4 pho omic og aph showing he inne pa o he clas s cu longi udinally. Each o hem
appea s di e en om he o he in e ms o mo phology bu we can obse e equen ly a pa o a da k
ma ix (dm) (b,e, ,g) and wi hin i a eas o di e en colo , some imes whi e (c), yellow/ ed (e, ,d) o
anspa en (b,e). Many samples p esen li le esicles and bubble s uc u es, indica ing degassing
p ocessing (c), me allic, alloy o e ac o y inclusions (a,g) some ime wi h eac ion ims (a). Ex e nal
g ey c us su ounding ela ed o ca bona ion is shown in igu e (d).
This likely occu s as XRF analyses conside also pu e SiO2 esidual glass, which was disca ded in
he analysis o he g ains. The glassy ma ix is he hos o Na, K, and Mg, elemen s which a e no
59
3.2 COMPARISON BETWEEN W E PLANTS IN NORTHERN ITALY
In his second in es iga ion he esul s on he i s in es iga ion on he Pa ma W E plan s a e discussed
wi h u he da a om 5 W E plan s om no he n I aly. XRD, XRF and TGA analysis we e
conduc ed o each g ain size; he XRF analysis showed highe concen a ions o PTE in he ine
g ain size and o his eason he g anulome ic classes < 4mm we e used o leaching es . The main
esul s we e:
1) a no able simila i y in he majo elemen composi ion, in spi e o he di e en loca ions and inpu
luxes;
2) a s ong di e ence in he con en o he amo phous phase, be ween he Fe a a and Fo lì-Cesena
incine a o s, espec o he o he s;
3) a pa ial con i m o he end be ween g ain size and composi ion ound in he i s pape , wi h
elemen s like Al and Fe showing di e en composi ion and g ain size ela ions in he 5 incine a o s;
4) a a ying leaching o he mino elemen s, among which PTE, wi h esul s ollowing a end and o
he same o de o magni ude in he samples om each incine a o ;
5) a gene al end whe e PTE a e eleased mo e in he smalle g ain size po ion, o en wi h alues
abo e egula o y limi s.
The esul s ob ained ha e been he subjec o an a icle cu en ly being submi ed. The a icle is
epo ed as pa ag aph 3.2.1. Fo simplici y, igu es and ables ha e been e-numbe ed ollowing he
s uc u e o his hesis.
3.2.1 G ain size and mine alogical cons ains on leaching in he bo om ashes om municipal solid
was e incine a ion: a compa ison on 5 plan s om No he n I aly
Au ho s:
Man o ani L1, De Ma eis C.1, T ibaudino M.2, Bosche i T.1, Funa i V.3,5, Dinelli E.4, Tolle
S.1,3, Pelaga i P.1
1Dipa imen o di Scienze Chimiche, della Vi a e della Sos enibili à Ambien ale (SCVSA),
Uni e si à di Pa ma, 43124 Pa ma
2Dipa imen o di Scienze della Te a, Uni e si à di To ino, 10124 To ino
3Consiglio Nazionale delle Rice che, Is i u o di Scienze Ma ine (ISMAR-CNR), 40129
Bologna
4Dipa imen o di Scienze Biologiche, Geologiche e Ambien ali (BiGeA), Uni e si à di
Bologna, 40126 Bologna
5Dipa imen o di Bio ecnologie Ma ine, S azione Zoologica An on Doh n, 80121 Napoli
Type:
A icle
Jou nal:
F on ie s
S a us:
Submi ed

60
Keywo ds: MSWI-BA, PTE, ma e ial cha ac e iza ion, leaching es , g ain size analysis
Abs ac
In oduc ion. Bo om ash (BA) om municipal solid was e incine a o (MSWI) a e cu en ly
classi ied by he Eu opean Was e Ca alogue as indus ial non-haza dous was e. To p omo e hei
euse, iden i ica ion and cha ac e iza ion o he hea y me als bea ing phases (bo h glass and
mine als), as well as hei wea he ing beha io mus be add essed o wha conce n he chemical
composi ion, mine alogical phases and in high concen a ions and pollu an s’ mobili y. An impo an
poin is wea he he esul s om a gi en plan can be gene alized.
Ma e ial and Me hods. In his wo k BA om 5 no he n I aly Was e o Ene gy (W E) plan s we e
so ed based on di e en g ain sizes. The inpu was e o he plan s is simila , coming om a cul u ally
homogeneous a ea, and wi h simila collec ion managemen . Fo each g ain size, a mine alogical,
chemical and physical cha ac e iza ion has been done using o X- ay luo escence (XRF), X- ay
powde di ac ion (XRD) and Rie eld e inemen , The mog a ime ic analyses (TGA) and leaching
es .
Resul s and Discussion. We ound ha o majo elemen s he a e age chemical composi ion o he
incine a o s is simila , wi h some di e ence in mino elemen s. Fe a a (FE) and Fo lì-Cesena (FC)
BA show po landi e, highe e ingi e and lowe amo phous han he To ino (TO) Pa ma (PR) and
Piacenza (PC) ones. This a ec s he pH and he elease and oxici y o he leacha es. In FE and FC
ashes e ingi e is no dissol ed, and we ha e low sulpha e, bu also Ni and Ba beyond eglemen a y
limi s, sugges ing ha Ni and Ba a e p esen as hyd oxides wi h po landi e, which dissol es. In TO,
PR and PC C and sulpha es a e beyond limi s, sugges ing ha C comes om dissolu ion in e ingi e.
Cu and Cl a e always beyond limi s; he dissolu ion o chlo ides accoun s jus o 30-35% o he
global Cl leacha e. We obse e ha in he assessmen o po en ial oxici y o he ashes mine alogy
has an e ec highe han he bulk chemical composi ion.
Bulk and leacha e composi ion show signi ican changes wi h g ain size, bu gene ally wi hin an o de
o magni ude. G ain size so ing, al hough use ul oge he wi h o he echniques is no by i sel able
o comply wi h he PTE isk le el.
1. In oduc ion
The wo ld gene a es 2.01 billion ons o municipal solid was e (MSW) pe yea , whe e i has been
es ima ed ha a leas 33% is no managed in an en i onmen ally sa e manne . On a e age, each
indi idual gene a es 0.74 kg/day bu wi h s ong egional di e ences. The global was e p oduc ion is
expec ed o g ow up o 3.40 billion ons by 2050 (Kaza e al., 2018).
61
Was e managemen in I aly is egula ed by he legisla i e dec ee n°152/2006, which implemen s main
Eu opean di ec i es on was e. Acco ding o he dec ee n°152/2006 MSW incine a ion esidues need
o be ea ed be o e hey a e disposed o . Land illing is he mos common me hod used o manage
MSW, bu land illing has also conce ns abou g oundwa e pollu ion and soil con amina ion. Among
he di e en was e managemen op ions, was e incine a ion is mos impo an and widesp ead: i
educes he olumes and weigh o he was e, and in W E plan s i also p o ides a bonus o ene gy
p oduc ion (Bawab e al., 2021) .
Incine a ion p oduces wo ypes o solid esidues: bo om ashes (BA) and ly ashes (FA). The BA a e
he solid esidues esul ing om he combus ion o household was e a he lowe ou le o he u nace,
a e cooling in wa e ank, whe eas he FA a e he blown ou ac ion. In gene al, BA a e abou 20%
o he o al was e mass, and he FA, abou 4% (Izquie do e al., 2002). FA in I aly a e usually excluded
om ecycling as hey con ain and elease se e al haza dous elemen s (Se oodeh Jah omy e al.,
2019).
The BA a e composed by a mine al ac ion (80–85%), e ous me als (5–10%), non- e ous me als
(2–5%), and unbu ned o ganic ma e (CEWEP, 2016). The chemical composi ion o he bo om ash
depends on he MSW eed cha ac e is ics and on he combus ion sys em; he con en o majo
elemen s esembles on a e age he con en o hese elemen s in he soil and li hosphe e. The con en
o mino and ace elemen s a ies depending on he plan ; o mos elemen s i is deple ed, and o
some like Zn, Pb, Cl i is highly en iched wi h espec o he equi alen a e age concen a ions ound
in he soil and li hosphe e (Dijks a e al., 2009). Compa ed wi h o he combus ion was e, BA is
highly en iched in Cu, Mn, Zn, Pb, C , and Ni (Izquie do e al., 2002). In a ci cula economy
pe spec i e, la ge quan i ies o BA can be conside ed as u ban mines, om which i could be possible
o ex ac and ecycle ma e ials and chemical elemen s. In his poin o iew, he chemical and
mine alogical cha ac e iza ion o BA is o pa amoun impo ance.
In he las 20 yea s a numbe o s udies in es iga ed he echnical and en i onmen al p ope ies, as
well as ecycling me hods, leaching beha io , geochemical and pe ological aspec s o BA. All hese
li e a u e da a s essed he s ong complexi y o he BA due o an in insic he e ogenei y o he
ma e ial caused by a) selec i e collec ion o household was e, b) choice o incine a ion echnology,
c) u nace echnology, d) cooling p ocesses, e) ma u a ion p ocesses (among o he s:Ze enbe gen e
al., 1998; Eusden e al., 1999; Meima and Comans, 1999; Pian one e al., 2004; Ginés e al., 2009;
del Valle-Ze meño e al., 2017; Dou e al., 2017; Alam e al., 2019).
An impo an poin deba ed by o he au ho s is he incomple e knowledge o he chemical, physical
and mine alogical composi ion o he BA, hus making any app oach o euse e y app oxima e (di
Gian ilippo e al., 2018; Hube e al., 2020).
62
Fo example, he ine i on pa icles mingled wi hin he mine al ac ion can ha dly be sepa a ed by
magne s and o m se e al compounds con aining hea y me als, which can po en ially be ecycled
(Wei e al., 2011b)
In ecen yea s, much esea ch has been conduc ed on he use o bo om ash as conc e e in cemen s
(Bawab e al., 2021; Kleib e al., 2021) in ce amic ma e ials (Ka amano e al., 2021; Zanelli e al.,
2021) and as ille s bi uminous mix u e (Suá ez-Macías e al., 2021). I appea s ha any such
applica ion equi es a ocus on he chemical and physical ea u es o he bo om ashes, gi ing
a en ion o hei s ong he e ogenei y, and o how hei mine alogy a ec s he elease o po en ially
oxic elemen s (PTE) in he en i onmen .
The cha ac e iza ion o was e om incine a o s in e ms o chemical and mine alogical a ia ion is
p elimina y o possible euse pa hs. A c i ical pa ame e was ound o be g ain size. I was shown ha
chemical composi ion changes wi h g ain size, and ha se e al PTE a e concen a ed in he ine
ac ions (Chimenos e al., 1999; Wei e al., 2011a; del Valle-Ze meño e al., 2017; Šyc e al., 2018,
2020). Mo e ecen in es iga ion, howe e , con end he abo e as a gene al ule, showing o a gi en
elemen di e ences in g ain size s composi ion in di e en incine a o s (Ca iglia e al., 2019;
Logino a e al., 2019; Hube e al., 2020; Man o ani e al., 2021). A limi in he abo e in es iga ions
is he lack o a quan i a i e mine alogical composi ion wi h g ain size, oge he wi h leaching es s o
de e mine he possible elease o PTE.
In his wo k he chemical, physical and mine alogical analysis o BA om 5 plan s loca ed in
No he n I aly has been done. The a eas show simila MSW p oduc ion, coming om a cul u ally
homogeneous a ea, and wi h simila collec ion managemen . This will educe he bias o possible
di e ences in he inpu , which a ec such compa ison be ween incine a o s. The samples we e so ed
acco ding o he pa icle size and hen analyzed o unde s and he a iabili y coming om his
pa ame e . XRD, XRF, TGA we e pe o med on each po ion, and ollowed by leaching es s. G ain
size, elemen al composi ion, and leacha e p oduc s ha e been s udied by PCA analysis.
The aims o his wo k a e: a) o desc ibe he mine alogical and chemical a iabili y be ween he
bo om ashes om di e en W E acili ies, a ising om plan pe o mance du ing incine a ion and
wea he ing; b) o p o ide gene al ela ions be ween g ain size and composi ion, and be ween he
di e en elemen s, o bulk and leacha es, in o de o assess he po en ial o g ain size so ing o a
highe alue use o he ashes; c) o p o ide new sugges ions o o esee po en ial leaching om he
mine alogical composi ion o he ashes.
2. Ma e ial and Me hods
2.1 MSWI bo om ash sampling and so ing
63
The samples come om 5 W E plan s loca ed in no he n I aly, 3 o hem owned by I en Ambien e
SpA (Pa ma, To ino and Piacenza, he ea e PR, TO and PC) and 2 by He ambien e Spa (Fe a a and
Fo lì Cesena, he ea e FE and FC) (Figu e 3.2.1.1). Table 3.2.1.1 summa izes o each plan he
s a ing da e o he ac i i y, he ype o was e inpu ( ons/yea ) and he o al weigh o BA p oduced.
Figu e 3.2.1.1: geog aphical dis ibu ion o WTE plan s in es iga ed in his wo k.
All he plan s analyzed ha e a g a e u nace echnology ha bu ns he was e o wo o h ee hou s a
empe a u es be ween 750 °C and 1000 °C. The inpu was e includes abou 80% o undi e en ia ed
ac ion o sepa a e collec ion (abou 80%) and abou 20% om special non-haza dous was e
(indus ial and household was e, sewage sludge, ceme e y, biomedical was e, e c.). Only MSWI a e
bu n in he Fo lì plan (I en Ambien e S.p.A., 2018; He a Ambien e S.p.A., 2020).
The BA sampling om he plan s was ca ied ou du ing a ypical day o he p ocess ac i i y in
di e en pe iods as epo ed in Table 3.2.1.1. Samples we e andomly aken om a 2-3 m high
s ockpile which is ep esen a i e o mo e han one mon h o accumula ion. The homogenei y was
checked by making X- ay di ac ions on epea ed days, wi hou showing any signi ican di e ence.
The samples we e aken in May 2019 in PR, TO and PC W E plan s, and in Ap il 2020, du ing he
pandemic lockdown, in FE and FC. Abou 5 kg o BA samples we e collec ed om each plan . Be o e
64
he analysis, he ashes we e mixed, d ied in an o en a 50°C o 24 h and sie ed o di e en size
classes. The sequen ial sie ing (Φ: 16, 8, 4, 2, 1, 0.5, 0.3, 0.2 and 0.63 mm) was pe o med acco ding
o he Eu opean s anda ds o agg ega es EN 933–2(En e Nazionale I aliano di Uni icazione, 2020).
W E plan
ope a ing
since (using
his se up)
was e inpu ( ons/y)
% o he
was e
ype
o al was e
inpu
BA
p oduc ed
( ons/y)
da a
ela ed
o
sampling
da e o
his wo k
PARMA
2014
undi e en ia ed municipal solid
was e (MSW)
126 317
79
159 832
32 904
2019
2019
special was es (SW)
33 515
21
PIACENZA
2002
undi e en ia ed municipal solid
was e (MSW)
110 041
96
114 231
21 135
2018
2019
special was es (SW)
4 190
4
TORINO
2014
undi e en ia ed municipal solid
was e (MSW)
457 603
81
562 269
118 969
2019
2019
special was es (SW)
104 666
19
FERRARA
2008
undi e en ia ed municipal solid
was e (MSW)
69 598
53
131 894
27 021
2020
2020
special was es (SW)
62 296
47
FORLI
2008
undi e en ia ed municipal solid
was e (MSW)
119 215
100
119 215
53 308
2020
2020
Table 3.2.1.1: was e inpu and ou pu (only o BA) o each sampled W E plan . Municipal Solid Was e:
household and simila was e; Special Was e: was e om municipal sewage ne wo k and ea men , municipal
cons uc ion and demoli ion was e, sani a y and ceme e y was es (Da a om: He a Ambien e S.p.A., 2020b,
2020a; I en Ambien e S.p.A., 2018, 2020)
The cumula i e g ain size dis ibu ion cu es a e epo ed in Figu e 3.2.1.2. Agg ega es la ge han
3 cm we e emo ed o a oid loss o ep esen a i eness and dis o ion o he analy ical esul s.
Figu e 3.2.1.2: Cumula i e pa icle size dis ibu ion o bo om ashes o he 5 plan s analyzed. The dashed
lines epo he Fulle ’s cu es wi h n=0.4,0.5 and 0.6 ad dmax=20

65
2.2 XRD analysis
X-Ray powde Di ac ion (XRD) was pe o med on each sie ed ac ion. A B uke D2 Phase
powde di ac ome e was used, ope a ing a 30 kV and 10 mA wi h Cu Kα (λ = 1.54178 Å) adia ion.
The collec ions we e done a 2θ be ween 5 and 100°, s eps o 0.02°, and 1sec/s ep sampling ime. The
di ac ome e wo ks wi h θ-θ ocalizing geome y and akes ad an age o a solid s a e de ec o . A 30
pm sample o a ion was applied o minimize c ys al p e e en ial o ien a ion e ec s. The di ac ion
pa e ns we e iden i ied using he B uke so wa e EVA and he C ys allog aphy Open Da abase
(COD) (Table 3.2.1.2). GSAS 2 so wa e package (Toby and on D eele, 2013) was used o pe o m
Rie eld analysis and quan i y he majo c ys alline phases and he amo phous con en . High pu i y
Al2O3 co undum (10 w %) was used as in e nal s anda d. APPENDIX IV epo s he quan i a i e
in e p e a ion o XRD analysis wi h g ain size o each W E plan .
mine al phases
W E plan s
Name
Fo mula
PR
PC
TO
FE
FC
Calci e
CaCO₃
x
x
x
x
x
Va e i e
CaCO₃
x
x
x
x
x
Qua z
SiO2
x
x
x
x
x
C is obali e
SiO2
/
/
*
/
/
Ano hi e
Ca(Al2Si2O8)
x
x
x
x
x
By owni e
(Ca,Na)[Al(Al,Si)Si2O8]
x
x
x
x
*
Albi e
Na(AlSi3O8)
*
*
*
/
/
Py oxenes
g oup
ABSi2O6
/
/
x
/
/
Ake mani e
Ca2Mg(Si2O7)
*
*
*
x
x
Gehleni e
Ca2Al(AlSiO7)
x
x
x
*
*
E ingi e
Ca6Al2(SO4)3(OH)12 · 26H2O
x
x
x
x
x
Hyd ocalumi e
Ca4Al2(OH)12(Cl,CO3,OH)2 · 4H2O
x
x
x
x
x
Po landi e
Ca(OH)2
x
x
x
x
x
S ä lingi e
Ca2Al2SiO7 · 8H2O
x
/
/
/
/
Apa i e
Ca5(PO4)3(Cl/F/OH)
*
*
*
*
*
La ni e
Ca2SiO4
*
*
*
x
x
Tobe mo i e
Ca4Si6O17(H2O)2 · (Ca · 3H2O)
*
*
*
/
/
Sjog eni e
Mg6Fe2(OH)16(CO3) · 4H2O
/
/
/
*
*
Magne i e
FeFe2O4
x
x
x
x
x
Ema i e
Fe2O3
x
x
x
x
x
Table 3.2.1.2: XRPD iden i ica ion o bo om ash. The mine als a e a anged in he ollowing sequence: (x)
majo mine als (*) mino o ace mine als, (/) no ound o e y doub ul p esence.
66
2.3 XRF analysis
The bulk composi ion o each g ain size was measu ed using a wa eleng h dispe si e X- ay
luo escence spec ome e (XRF), Panaly ical Axios 4000, equipped wi h a Rh ube. Abou h ee
g ams o he ep esen a i e samples we e o en-d ied a 50° C, homogenized and milled wi h an aga e
ib a o y disk mill. Thin-laye p essed powde pelle s o XRF analysis we e p epa ed using a bo ic
acid binde . The ep oducibili y, he gene al accu acy h ough calib a ion cu e and co ec ions o
he da a a e he same used in o he wo ks (F anzini e al., 1972; Tolle e al., 2021). Majo , mino and
ace elemen s (SiO2, TiO2, Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, P2O5, As, Ba, B , Ce, Cl,
Co, C , Cu, Ga, H , La, Mo, Nb, Ni, Pb, Rb, S, Sc, Sn, S , Th, U, V, W, Y, Zn, Z ) concen a ions a e
calcula ed using a calib a ion cu e buil on a la ge numbe o ce i ied e e ence ma e ials and o line
co ec ion o Loss On Igni ion (LOI) alues. LOI, which is co ela ed wi h he in luence o humidi y,
o ganic ma e , and wa e , was g a ime ically es ima ed a e o e nigh hea ing he samples a 950°C
in a mu le u nace (Hei i e al., 2001)
2.4 The mo G a ime ic Analysis
The mal g a ime ic analyses we e conduc ed by means o a Pe kin Elme 8000 ins umen equipped
wi h a P -c ucible (sample mass app oxima i ely 3-5 mg) a a hea ing a e o 10 °C/min in he
empe a u e ange 35–800 °C. All he measu emen s we e un unde a cons an lux o d y ai
a mosphe e (30 mL/min).
2.5 Leaching es s and wa e elemen al analysis
S anda d leaching es s and analysis o he leacha es we e pe o med ollowing he UNI EN 12457-2
(En e I aliano di No mazione, 2004), a es o compliance o he leaching o g anula was e and
sludge, which in his case has been adap ed o bo om ashes assessmen . The es is based on a one
s age ba ch a a de ined liquid o solid a io o ma e ials wi h pa icle size below 4 mm. Samples
ha e hus emained in ul apu e wa e (Milli-Q ® 18.2 MΩ.cm a 25 °C and TOC < 5 ppb) o 24
hou s unde mechanical oscilla ion in a con olled en i onmen . The analysis o he leacha e samples
we e conduc ed using Ion ch oma og aphy (Me ohm Compac IC p o 881) o anions (Cl-, SO4-2, F-
, B -, PO43-), A omic abso p ion spec oscopy (The mo S Se ies AA Spec ome e ) o ca ions (Ca,
Mg, Na, K), and Induc i ely coupled plasma mass spec ome y (Pe kin Elme ICP-MS ELAN DRC-
e) o ace elemen s (Al, Ba, B, C , Co, Fe, Pb, Li, Mn, Mo, Ni, Se, S , Tl, Ti, V, Zn). Finally, he
me al ex ac ion ( om he solid o he leacha e) was calcula ed as Xlea/Xbulk *100 o each W E plan
in he g ain size < 2 mm, whe e Xlea is he analy ical de e mina ion o he a ce ain elemen on he
leacha e and Xbulk is he o al concen a ion o he solid by XRF.
67
3. Resul s and discussion
3.1 Pa icle size dis ibu ion
Figu e 3.2.1.2 shows he g ain size cu es o he samples. In all he BA samples he la ge ac ion
p e ails: below 1 mm he sie ed po ion ep esen s be ween 5 and 8 w .% o he o al mass, and 50%
o he mass does no pass he a 4 mm sie e. This was also ound in p e ious in es iga ions (del Valle-
Ze meño e al., 2017; Šyc e al., 2018; Ca iglia e al., 2019). An excep ion is he PC plan , whe e
he e is a highe pe cen age o ine and medium sized pa icles ( he g ains passage is almos 80% a
4 mm). I is no clea whe he his is due o he sampling me hodology o he in insic he e ogenei y
o MSWI esidues. In o de o es he ecyclabili y o BA in cemen i ious o mula ions, we compa ed
ou esul s wi h he op imum size dis ibu ion o conc e e acco ding o he Fulle cu e, which
ep esen s he op imal agg ega e dis ibu ion cu e in e ms o densi y and s eng h(Fulle and
Thompson, 1907). The Fulle cu e calcula es he op imum pe cen age o a gi en pa icle diame e d
as: P (d) =100(d/dmax)n. Th ee Fulle cu es we e calcula ed wi h an agg ega e maximum alue o
dmax = 20 mm, i.e. he maximum opening sie es used he e and n exponen ial ac o n = 0.4, 0.5 and
0.6. In no case he dis ibu ion alls comple ely wi hin he cu es, as he smalle dimensions a e
unde ep esen ed in ou sampling.
3.2 XRD
Tables 3.2.1.2 and APPENDIX IV show he mine alogical composi ion o he BA and hei
sepa a ed g ain size classes. The bulk mine alogical composi ion o he ashes o each incine a o
was ob ained om ha o each g ain size and hei p opo ion as:
ci,bulk= ci,j*wj/wbulk
whe e ci,j is he ac ion o he mine al (i) in he sie ed po ion (j) (as epo ed in APPENDIX IV),
wj he weigh o he sie ed po ion and wbulk, he weigh o he sum o he sie ed po ions.
The mine als epo ed in APPENDIX IV a e hose mos p esen , whose abundance could be e ined
by Rie eld analysis. A numbe o mino phases is also p esen , which ei he showed e y ain peaks
in XRD o could be de ec ed jus om mic op obe analysis (Bayuseno and Schmahl, 2010; Man o ani
e al., 2021). Du ing Rie eld analysis i was shown ha he inclusion o a highe numbe o phases
leads o e inemen ins abili y, so ha a comp omise was necessa y be ween he numbe o phases o
be included and he numbe ha could be e ined. In some cases, iden i ica ion o mine al phases was
doub ul due o he o e lap o iden i ica i e e lec ions associa ed o ce ain peaks (Table 3.2.1.2).
Mos e iden is he amo phous con en , which is highe in he BA o he h ee plan s (TO, PR, PC)
so as ha i o e akes he en i e quan i a i e o c ys alline componen . In hese plan s, he amo phous
is o e 75% on a e age, and anges in di e en g ain size be ween 67 and 88 w %. In he plan s o
68
FE and FC, ins ead, bulk amo phous is, on a e age, less han 35% (depending on g ain size be ween
7 and 55w %). Fu he mo e, he e is a sligh in e se co ela ion be ween he loga i hm o he g ain
size and he amo phous con en , wi h R2 = 0.64, 0.53, 0.41, o PR, PC, TO, espec i ely. Fo FE and
FC he co ela ion is no signi ican (p>0.05) ( o s a is ical alue see APPENDIX VII).
The la ge amoun o amo phous is common in bo om ashes (among o he s Eusden e al., 1999;
Bayuseno and Schmahl, 2010; Ca iglia e al., 2019; Logino a e al., 2019; Šyc e al., 2020). Mo e
ecen ly Man o ani e al. (2021) showed ha se e al amo phous phases cha ac e ized by a di e en
composi ion and o ma ion, and likely mic o-s uc u e a e p esen a he han a single homogeneous
amo phous phase. Residual glasses coming om he inpu was e a e mos p esen in he la ge g ains,
whe eas in ine g ain and in some a eas o agg ega es, pa ly mel ed glasses a e also p esen .
Mic op obe analyses on hese glasses po ion showed ha hey a e di e en in composi ion; in
gene al, hey coexis wi h c ys als in eu ec oid condi ions, wi h he local composi ion depending on
me al ( ansi ion, alkali and alkali ea h) con en .
The lowe quan i y o amo phous ma e ial in FE and FC occu s oge he wi h highe calci e, qua z
and eldspa . Also e ingi e con en is highe in FE and FC han he o he 3 plan s sampled, indica ing
a p obable g ea e eac i i y o hese ashes in he aging p ocess. FE and FC showed he p esence o
la ni e and po landi e, p obably due o he high Ca con en and asc ibable o ca bona ion eac ion
and cemen i ious ma e ial in he inpu eed.
Among mine als, qua z, calci e, melili es, i on oxides and some al e a ion p oduc s such as sulpha es,
chlo ides, and hyd a ed mine als a e ubiqui ous. An in e se ela ion wi h g ain size is ound in calci e,
mainly in TO and PR incine a o s (R2=0.95 and 0.82, espec i ely) and less in PC and FC (0.53 and
0.45). In FE bo om ashes, he ela ion is no signi ican , bu he la ge size shows a much lowe
calci e con en han he ine po ion. Calci e p obably de i es om seconda y ca bona ion, du ing
wea he ing in he empo a y s o age si e, bu we do no exclude ha he highe calci e con en in FE
and FC may come om an un inished deca bona ion p ocess du ing he mal decomposi ion.
Po landi e, Ca(OH)2 is ound only in he BA ashes om FE and FC as a p oduc o ehyd a ion o
CaO. The Ca-oxide o ms a a empe a u e o app oxima i ely 700 °C a an ini ial a mosphe ic pa ial
p essu e (0.04 a m) and om he de-ca bona ion eac ion (C iado e al., 2018):
CaCO3 => CaO + CO2(g)
In FC po landi e co ela e wi h he amo phous con en (R2= 0.72). Such posi i e co ela ion is also
ound, albei wi h lowe e idence also in wi h Fe a a (R2= 0.34).
E ingi e, hyd ocalumi e and s ӓ lingi e we e o med du ing wea he ing. E ingi e and
hyd ocalumi e a e ubiqui ous, whe eas s ӓ lingi e is ound only in he PR plan . E ingi e in TO is
posi i ely ela ed o calci e and hyd ocalumi e (R2= 0.82 and 0.83, espec i ely), and shows a
75
3.5 Leaching Tes s
Leaching es s we e done on pa icle sizes below 2 mm, as XRF analyses showed ha hey a e iche
in PTE. The leaching was done on pa icles o di e en size, and hei a iabili y was analyzed by
PCA. The esul s a e epo ed in APPENDIX VI and APPENDIX IX.
PCA analysis shows ha he wo majo componen s desc ibe mo e han 80% o he a iabili y in all
W E. A numbe o ions, among which Cl, K, Li, Na and Cu show an opposi e end espec o g ain
size, i.e. show highe leaching in smalle g ain sized samples. SO42- ollows Cl in TO, PR, PC and
FC. In FE and FC he sulpha es leached a e one o de o magni ude less han in o he incine a o s. Ni
and C ollow Cl and sulpha es in TO, PR and PC, bu no in FE and FC. Pb does no ollow a de ini e
end, wi h li le change wi h g ain size. Al is leached in signi ican amoun only in TO, PR and PC,
bu no in FE and FC.
Ma ked di e ences in leaching beha io ha e been ound be ween he wo di e en owne
co po a ion ha is IREN o PR, PC and TO and HERA o FC and FE.
Al hough gene ally he leaching is highe in smalle g ain size po ion, g ea di e ence, wi hin one
o de o magni ude, is ound. Highe di e ences a e obse ed be ween W E plan s.
Figu e 3.2.1.8: pe cen age o eleased elemen s calcula e as (Xbulk/Xlea)*100 o each W E plan in he g ain
size < 2 mm

76
Wi h espec o a gi en pa icle size, he leaching o an elemen has been compa ed o he o al con en
in he bulk sample ( om XRF analysis) and calcula ed in pe cen age (all e e ed o mg/kg o
ma e ial). The mos eleased elemen is Cl wi h a elease pe cen age o abou 70/90%, highe in he
ine ac ion (Figu e 3.2.1.8 and 3.2.1.9, APPENDIX VI).
Figu e 3.2.1.9: a) co ela ion be ween he leached Na++K+ s Cl- and b) SO42- s Ca2+ (mg/l).
The ex ac ion e iciency in he smalle po ion is almos wice ha in he la ge one. In ag eemen
wi h Alam e al. (2020) we sugges ha Cl is p esen in e y soluble sal s, like NaCl and KCl,
dispe sed on he su ace o he g ains. This sugges ion is con i med by he linea ela ion ound in
leached Na+K wi h Cl (Figu e 3.2.1.9 a), whe eas such ela ion does no exis in he sample
composi ion de e mined by XRF as mos Na and K a e likely caged wi hin he amo phous and
silica es s uc u es. Howe e , he amoun o chlo ides in leacha e a e conside ably g ea e han he
Na+K alue (and no in a 1:1 a io), sugges ing ha he elease o Cl is no only a ibu able o he
dissolu ion o he Na/K sal s. The e o e, no di ac ion peaks a ibu able o Na,KCl a e ound in XRD
analysis, sugges ing ha no all he Cl is bound o Na and K in sal s, and ha a signi ican elease o
Cl may be o igina e by he dissolu ion o e ingi e.
The e o e, p obably he con ibu ion o e ingi e dissolu ion is mino , due o he e y simila a io in
Na+K/Cl in he 5 plan s, in spi e o he di e en amoun and solubiliza ion o e ingi e (Figu e
3.2.1.10).
EDS analyses o he ashes om PR, (Man o ani e al., 2021) showed ha Cl is o en associa ed wi h
silica e glassy phases. We sugges he e o e ha chlo ide is mos eleased by dissolu ion o weakly
bonded Cl a he su ace o he amo phous phases. This would explain he highe leaching in smalle
g ains, wi h highe su ace.
77
All es s exceeded he legal limi s o Cl (Legisla i e Dec ee 152/06) sugges ing ha washing and
selec ion o la ge g ains may be combined echnique o educe Cl o a co ec euse.
S shows a elease, abou 30% o PR, PC and TO and 3% o FE and FC, wi h no dependence on he
pa icle size. S is p esen in he e ingi e s uc u e which is obse ed in XRD in all he plan s,
especially in FE and FC. Howe e he elease in SO42- is lowe in he wo HERA W E plan s, whe eas
he Ca is highe (Figu e 3.2.1.9 b). Mo eo e , Al is eleased by a leas wo o de o magni ude less
in HERA han in IREN plan s. Ano he ele an di e ence is ha he measu ed pH in he leached
IREN plan s is be ween 10 and 11, whe eas in he HERA plan s i a ies be ween 12 and 12.5.We
sugges ha in he HERA plan s, he dissolu ion o po landi e, which is absen in he IREN plan s,
gi es ise o a basic en i onmen , whe e e ingi e is less p one o dissolu ion. In he IREN plan s,
e ingi e dissol es, wi h sulpha e and Al hyd oxide solubiliza ion.
O he elemen s like Mg and Fe do no show a signi ican leaching, indica ing ha hey a e bonded in
non-soluble oxide o silica e s uc u es.
Figu e 3.2.1.10: end o he Na++K+, Cl- and Na+K/Cl in he leacha e in unc ion o he g ain size (< 2mm)
o he 5 W E plan s.
78
The di e en mine alogy in IREN and HERA plan s, and he consequen di e en leaching in majo
elemen s has an e ec also on mino elemen s. Mino elemen s a e o en p esen in solid solu ion
wi hin phases mo e o less p one o dissolu ion a di e en pH, and he dissolu ion o he hos phases
eleases also he exsol ed elemen . The e o e he elease in mino elemen s is di e en in he di e en
W E plan s, o en by wo o de o magni ude. In a plan he leaching could be abo e legal limi s,
whe eas in o he s i could be no (Table 3.2.1.3).
Elemen s
Cl-
SO42-
F-
PO43-
Ba
Cu
Zn
As
Be
Co
Ni
V
Cd
C
Pb
Se
Legal Limi s
100
mg/l
250
mg/l
1.5
mg/l
2 mg/l
1mg/l
0.05
mg/l
3
mg/l
50
ug/l
10
ug/l
250
ug/l
10
ug/l
250
ug/l
5
ug/l
50
ug/l
50
ug/l
10 ug/l
W E plan s
g ain size
(mm)
mg/l
ug/l
PR
0.063 - 0.2
703
438
0
0
0.04
0.12
0.06
0
0
0
8
2
0
458
6
17
PR
0.2 - 0.3
678
420
0
0
0.04
0.09
0.06
0
0
0
8
2
0
354
0
17
PR
0.3 - 0.5
463
321
0
0
0.04
0.07
0.06
0
0
0
7
2
0
248
2
13
PR
0.5 - 1
391
267
0
0
0.05
0.05
0.04
0
0
0
8
2
0
212
4
19
PR
1 - 2
319
303
1.0
0
0.04
0.04
0.05
0
0
0
4
2
0
198
2
8
PC
0.063 - 0.2
993
327
4.5
0
0.08
1.15
0
0
0
0
4
2
0
119
4
62
PC
0.2 - 0.3
887
315
0
0
0.06
1.17
0
0
0
0
2
2
0
105
2
56
PC
0.3 - 0.5
662
253
11.4
0
0.06
0.88
0
0
0
0
2
2
0
74
2
46
PC
0.5 - 1
547
236
3.0
8
0.08
0.95
0
0
0
0
38
2
0
75
59
32
PC
1 - 2
428
173
3.9
0
0.04
0.36
0
0
0
0
0
0
0
31
0
34
TO
0.063 - 0.2
1170
756
0
0
0.09
5.31
0.11
0
0
11
57
4
0
306
19
15
TO
0.2 - 0.3
855
677
0
0
0.08
4.08
0.06
0
0
6
44
6
0
229
17
11
TO
0.3 - 0.5
632
457
0
0
0.07
3.36
0
0
0
6
42
6
0
219
33
13
TO
0.5 - 1
574
438
4.6
0
0.07
3.39
0.07
0
0
4
40
8
0
171
15
13
TO
1 - 2
436
359
4.3
1
0.06
3.43
0.12
0
0
4
23
13
0
147
25
11
FE
0.063 - 0.2
1064
59
1.8
0
5.53
0.53
0
0
0
0
15
6
0
6
44
21
FE
0.2 - 0.3
807
30
3.4
0
4.52
0.39
0
0
0
0
15
4
0
4
33
19
FE
0.3 - 0.5
741
42
7.7
0
2.95
0.36
0
0
0
0
16
2
0
6
33
14
FE
0.5 - 1
584
20
3.4
0
1.80
0.30
0
0
0
0
17
2
0
4
36
15
FE
1 - 2
528
18
6.4
0
1.45
0.32
0
0
0
0
15
2
0
11
29
13
FC
0.063 - 0.2
1043
5
0
0
38.53
1.05
0
4
0
2
19
27
0
31
13
31
FC
0.2 - 0.3
919
15
4.6
0
37.32
0.89
0
2
0
2
17
15
0
27
13
20
FC
0.3 - 0.5
779
13
15.5
1
25.20
0.93
0
0
0
2
19
10
0
23
16
10
FC
0.5 - 1
695
45
5.1
4
12.50
0.88
0
0
0
2
21
8
0
37
55
14
FC
1 - 2
608
47
5.1
0
0.80
0.74
0
0
0
2
21
6
0
41
10
14
Table 3.2.1.3: leaching es esul s o elemen s subjec o egula ion o plan s (d.lgs 156/2006). In ed,
concen a ions exceeding legal limi s.
Fo ins ance, sulpha e and C a e abo e egula o y limi s only in IREN BA, bu Ba and Ni (wi h he
excep ion o TO) only in he HERA plan s. S leaching is obse ed in high pe cen ages in FE and FC
(10-15% o he bulk), and less in he IREN plan s (4-6% in TO and 1-2% in PR and PC). A likely
in e p e a ion is ha C could ha e a signi ican concen a ion in e ingi e, which is dissol ed in
79
IREN plan s, whe eas Ba, Ni and S could exchange wi h Ca in signi ican amoun in po landi e,
which is dissol e in HERA plan s.
Zn and Mg a e eleased only in he TO and PR plan s, possibly in ela ion wi h e ingi e dissolu ion.
In TO he leaching o SO4, Co, Cu, Mg and Zn is highe han in o he plan s, and in PC B and Mo
show highe leaching. These di e ences, which a e mo e han one o de o magni ude look speci ic
o an W E, o a leas o he analyzed sampling om ha plan .
Cu, C and Ni a e, among he PTE, he mos eleased in all plan s wi h alues below 0.5%, excep o
TO whe e he Cu s ands a 3%. On he o he hand, he elease o Ti, Pb and Zn is ela i ely low
(<0.01%), ne e exceeds law limi s (Legisla i e Dec ee 152/06) sugges ing hei p esence in a non-
soluble s uc u e, like glass o silica e mine als.
4. Conclusions
The bo om ashes om he W E plan s show an a e age composi ion ema kably simila in majo
elemen s, jus wi h highe i on in TO, and lowe Si/highe LOI in PC. The chemical composi ion o
majo and mino elemen s changes wi h g ain size, bu wi hin an o de o magni ude and simila ly in
he di e en plan s. The simila BA composi ion could be ela ed o a simila was e managemen
app oach in he a ea.
The mine alogy is di e en be ween HERA (FE and FC) and IREN (TO, PR and PC) BA. In he
o me we ha e lowe amo phous and highe po landi e and e ingi e, in he la e we do no ha e
po landi e and he amo phous phases a e be ween 60 and 90%. This a ec s leaching, which occu s
in di e en basic en i onmen : he leacha es show highe sulpha e and Al in IREN plan s, and lowe
sulpha e-highe Ca in HERA plan s. Leaching up o wo o de s o magni ude lowe in Ba and S , and
highe in C occu s in IREN. The balance o Cl leaching shows ha alkaline chlo ides accoun jus
o abou 30-35% o he global Cl, a ac ion which does no show signi ican changes wi h g ain size
and be ween W E, and ha is simila o he indings o Alam e al. (2020).
Composi ion and leaching is o mos elemen s size dependen , bu almos in a iably wi hin an o de
o magni ude. Some elemen s like Cl, Zn, S, and he LOI dec ease wi h g ain size, bu o o he PTE
like Ni, C , Co and Pb his is no a ule. Leaching inc eases in smalle g ains o almos any elemen ,
bu again wi hin an o de o magni ude, whe eas be ween W E plan s we ind highe a iabili y in
leaching e iciency. F om a ci cula economy pe spec i e, euse o BA as a supplemen a y ma e ial
in conc e e is possible: he p esence o cemen ela ed mine als such as po landi e in FE and FC
suppo s euse in he conc e e, acili a ing he se ing and ha dening eac ions. Howe e , signi ican
concen a ions o Cl and S, especially in he ine g ain size, could be disad an ageous o cemen
applica ion and a p e- ea men be o e applica ion as cemen bind could be en isaged. G ain so ing
80
could be use ul in cases whe e leaching o he la ge g ain size alls below he legisla i e limi s o a
gi en elemen , while he smalle g ains do no , like C in PC and Cu in PR. I could be mo e p o i able
o gain acquain ance wi h he mine alogical and chemical dissolu ion beha io o he BA om a gi en
plan being he di e ences in he leaching o mino elemen s look mo e dependen o he mine alogy
han o g ain size.
Au ho con ibu ions
LM, MT: concep ualiza ion, me hodology, da a collec ion, da a calcula ion, w i ing–o iginal d a ,
and w i ing– e iew and edi ing. CDM, PP, ED, ST, VF, TB: me hodology, da a collec ion, da a
cu a ion, edi ing. LM, MT, CDM, PP, ED, ST, VF, TB ha e ead and ag eed o he published e sion
o he manusc ip

81
3.3 PTE SPECIATION: COMBINED SEM-EDS ANALYSIS, XRF AND XANES BY
SYNCHROTRON RADION STUDY
The ocus o his hi d wo k was PTE (Pb, Cu, Zn, Ni, Co and C ). Fo his eason, BA sampled om
he Pa ma was e- o-ene gy plan (0.5 - 1mm g ain size class), was s udied h ough a mul i- echnical
app oach. P e iously, as shown in he i s wo pape s, his pa icle size class was analysed by
di ac ion and luo escence echniques o gain an o e iew o he chemis y and mine alogy o he
ma e ial. Subsequen ly, some BA g ains we e analysed by SEM - EDS and XRF mapping and
XANES analysis conduc ed by synch o on acili y. In his way, in o ma ion was ob ained ega ding
no only he mine alogical en i onmen in which he PTE a e housed bu also hei oxida ion s a e,
in o ma ion o c ucial impo ance in assessing he po en ial oxici y o he ma e ial unde s udy. F om
he esul s ob ained, i can be seen ha he chemical elemen s analysed a e p esen in di e en
chemical o ms, especially zinc, which u ns ou o be he elemen ound in a g ea e a ie y o
mine alogical phases bu no in me allic o m. Ch omium has ne e been ound in +VI oxida ion
s a e, i s mos oxic o m. In gene al, PTE has been ound in he o m o me al (shee o alloy), oxide
(o hyd oxides), ca bona es, sulpha es, silica es, o as subs i u ed in o he c ys al s uc u es o
amo phous ma ices.
The esul s ob ained a e coming om an a icle ha is in he p ocess o being submi ed. The a icle
is epo ed as pa ag aph 3.3.1. Fo simplici y, igu es and ables ha e been e-numbe ed ollowing
he s uc u e o his hesis.
3.3.1 PTE specia ion in Bo om Ashes om Municipal Solid Was e Incine a o : a combined
SEM-EDS, XRF and XANES by synch o on adia ion s udy
Au ho s:
De Ma eis C.1, Pollas i S.2, Man o ani L.1, T ibaudino M.3
1Dipa imen o di Scienze Chimiche, della Vi a e della Sos enibili à Ambien ale (SCVSA),
Uni e si à di Pa ma, 43124 Pa ma
2Ele a Sinc o one T ies e S.C.p.A., 34149 T ies e
3Dipa imen o di Scienze della Te a, Uni e si à di To ino, 10124 To ino
Type:
A icle
Jou nal:
Science o To al En i onmen
S a us:
Submi ed
82
Abs ac
Po en ial Toxic Elemen s (PTE) in Municipal Solid Was e Incine a o Bo om Ash (MSWI-BA) may
be oxic depending o hei oxida ion s a e and mine alogical en i onmen . In his wo k, C , Ni, Pb,
Co, Zn and Cu chemical specia ion a e in es iga ed on BA om Pa ma Was e o Ene gy (W E) plan
by means o SEM-EDS, µ-XRF and XANES measu emen s by synch o on adia ion. This mul i-
echnique app oach allowed o examine PTE p o iding a gene al pic u e o mine alogical and
chemical p ope ies such as he oxida ion s a e. SEM-EDS analyses show he p esence o Zn and Pb
in mine als and in glass ma ix. C oxide and ch omi e has ound whe eas Cu and Co a e p esen as
me al inclusions o alloy. µ-XRF mapping e eals ha Cu, Ni and C a e gene ally oge he wi h Na,
K and Si sugges ing hei p esence in glass ma ix. XANES spec a show ha Cu has a a iable
oxida ion s a e sugges ing i s p esence as oxide, hyd oxide, ace a e and me al o m. Zn is mainly in
he +II oxida ion s a e con i ming he SEM-EDS da a. C has been ound always as +III, whe eas he
+VI oxida ion s a e was ne e iden i ied. Pb spec a ha e a good ma ch wi h oxides. Ni and Co we e
ound ei he as oxides and in me al o m.
G aphical abs ac
83
Keywo ds
BA-MSWI, PTE, Chemical-mine alogical cha ac e iza ion, XANES, specia ion, leaching
1. In oduc ion
A conside able inpu o an h opogenic ma e ial in he en i onmen is gi en by was e. In 2016, wo ld
was e p oduc ion was equal o 2.01 billion ons and due o economic and demog aphic g ow h will
each he 3.40 billion ons in 2050 (Kaza e al., 2018).
The was e can be sen o ecycling, compos ing, incine a ion p ocesses o deposi ed in land ills. A
conside able amoun o was e, as much as 11% o he global p oduc ion, is incine a ed (Kaza e al.,
2018). In indus ialized coun ies, he incine a ion is en us ed o W E plan s, which eco e ene gy
as hea and/o elec ici y h ough con olled combus ion o MSW.
FA and BA a e he main ou pu s o W E p ocesses. FA a e classi ied as haza dous was e and
cons i u e 4% o MSW mass, while BA a e non-haza dous was e and ep esen 20% o MSW mass
(Be olini e al., 2004; Izquie do e al., 2001; Nazionale, 2002).
BA a e o med by an ex emely complex and he e ogeneous mine al ac ion. In ecen yea s se e al
s udies aimed o cha ac e ize BA om a chemical, geochemical, mine alogical and physical poin o
iew (Alam, Schollbach, an Hoek, e al., 2019; Assi e al., 2020; Bayuseno & Schmahl, 2010;
Ca iglia e al., 2019; Hube e al., 2020; Logino a e al., 2019; Man o ani e al., 2021).
BA a e made o silica es, ca bona es, hyd a ed mine als, sulpha es, phospha es, oxides and an
amo phous componen ha in he la ge pa icle size classes can be up o 80% - 90% o he global
con en (Alam, Schollbach, an Hoek, e al., 2019; Assi e al., 2020; Bayuseno & Schmahl, 2010;
Ca iglia e al., 2019; Inkaew e al., 2016). The majo elemen s a e Si, Ca, Al, Mg, Fe, K, S, P and Na
whe eas among he mino ew po en ially oxic elemen s (PTE) such as Pb, Cu, C , Zn and Ni a e
ound (Alam, Schollbach, an Hoek, e al., 2019; Ca iglia e al., 2019; Funa i e al., 2015; Man o ani
e al., 2021).
Wi h espec o he global Ea h C us composi ion, Dijks a e al. (Dijks a e al., 2019) showed an
en ichmen in Ca, S and P, and sligh ly less in Si. To no e, PTE a e s ongly en iched espec o he
Ea h C us . This poses a bias in e-using BA due o he possible elease o PTE in en i onmen .
Se e al in es iga ions on he leaching beha iou o BA we e done, demons a ing ha PTE elease is
majo in ine g ain size because o bo h he pa icle dimension and he g ea p esence o wa e -
soluble mine alogical phases such as e ingi e and hyd ocalumi e (Alam, Schollbach, an Hoek, e
al., 2019; Ca iglia e al., 2019; Feng e al., 2007; Hube e al., 2020; Logino a e al., 2019; Man o ani
e al., 2021; Šyc e al., 2020; Wei e al., 2017; Yao e al., 2012).
84
The mobili y o an elemen owa ds an en i onmen al ma ix is s ic ly connec ed o chemical and
mine alogical cha ac e is ics: PTE in silica es o glasses a e eleased only a e a s ong acid a ack,
whe eas PTE in soluble phases may be easily eleased in he en i onmen . The e o e, se e al au ho s
ca ied ou sequen ial ex ac ions o in es iga e he associa ion be ween elemen s, c ys alline o
amo phous phases and hei leaching beha iou (Ab amo e al., 2018; Alam, Schollbach, an Hoek,
e al., 2019; Gooda zi & Huggins, 2001; Habe l & Schus e , 2019; Zhu e al., 2018).
Howe e , due o he complexi y o he ma e ial and he low concen a ion o PTE i is di icul no
only o ob ain an unambiguous co espondence be ween mine alogical and chemical in o ma ion bu
also o analyse he PTE a a de ailed scale, de e mining i s concen a ion and oxida ion s a e in he
di e en phases. This in o ma ion is c ucial o p edic and assess he po en ial elease and oxici y,
bu also o a aluable euse o BA (Rissle e al., 2020).
Synch o on-based XAS is one o he echniques ha can be used o in es iga e he chemical
specia ion o elemen s. The main ad an age o XAS is o de e mine he local a omic en i onmen and
oxida ion s a e o a gi en elemen . I is a e y sensi i e me hod, able o in es iga e elemen s also in
low concen a ion.
In li e a u e, he e a e ew s udies in he use o synch o on-bases XAS o MSWI in es iga ion. In
de ails, he mos pa o he da a ocused on Cu and Zn specia ion in FA (Hsiao e al., 2001, 2002,
2006), less on BA (Lassesson & S eena i, 2013; Rissle e al., 2020; S eena i & No én, 2008; Tibe g
e al., 2021) and no da a a e ound on o he s c i ical elemen s like Pb, C and Ni.
A limi in XAS me hods ega ds he lack o analy ical da a on he o he elemen s p esen in he same
poin . The e o e, he ex u al in o ma ion, like c ys al size, clus e ing, shape and/o inclusions o o he
phases in he a eas o analysis is los . This a ec s he eliabili y o he XAS analyses in showing he
dis ibu ion o he di e en phases in he sample. Synch o on adia ion-based mic o-XANES
oge he wi h mic o-XRF p o ides a powe ul al e na i e. Wi h a na owly ocused beam, sized as
li le as 50µm2, mic o-XRF analysis shows he local composi ion, wi h a sensi i i y down o he ppm
o he mino elemen s. The dis ibu ion o he PTE can be e ealed, and in chosen poin s he XANES
analysis can be done, showing he local en i onmen o speci ic elemen s.
Mic o-XRF and XANES we e combined in en i onmen al and cul u al he i age s udies, whe e an
he e ogeneous ma ix is p esen (Kos omi sopoulou Ma ke ou e al., 2021; Liu e al., 2020), bu no
in BA om incine a o ye .
The no el y o he p esen s udy is o p esen o he i s ime he combined mic o-XRF and XANES
da a on BA, wi h he aim o de e mine no only he chemical o m and specia ion o PTE, bu also
hei ex u al dis ibu ion and associa ion wi h o he elemen s. SEM-EDS analyses ha e been
pe o med on he same s udied sample, as well. In espec wi h mic o-XRF, he analy ical esolu ion
91
Figu e 3.3.1.2 SEM-BSE image o g ains wi h PTE: a) Willemi e-ha dys oni e assemblage (willemi e whi e,
ha dis oni e g ay); b) ZnO (whi e), o e g owing non s oichiome ic Zn bea ing gehleni e (g ay); c) Cu-Sn
oxidized alloy (whi e); d) Zn-Mn oxide (whi e); on he le o he image we ind Ca-ca bona e, g ay, and
glass, da k g ay; e) FeC O3, whi e, coexis ing in a composi e g ain wi h Ca- ich glass (ligh g ey) and
alumina (da k g ay ound phases); ) Ca-plumba e (Ca2PbO4), shown by whi e squa ed g ains, oge he wi h
lime (ligh g ay), and silica e glass; g) Pb wi h TiO2 oxide (whi e ounded g ains) ; h) glass ma ix wi h C -
oxide inclusions (whi e poin s).

92
The embedded g ains a e gene ally made by a co e, wi h he shape nea ly appea ing om he epoxide
in BSE images. A im usually bo de s he co e, wi h smalle c ys als embedded in a da ke ma ix.
SEM-EDS analysis on he ims could be done jus in ew la ge c ys als, inding ha hey ha e a
di e en composi ion om he co e, i.e., among o he s, Ca-ca bona e, phospha es, esidual
plagioclase, sulpha es and chlo ides.
µ-XRF maps show ha some elemen s, namely Ca and Si, bu also Mg, Al, Fe, P, C , Ti, Co, and Pb
a e gene ally p esen wi hin he co e o he g ains. Zn and Cu a e ound bo h in he ims and in he
co e, whe eas o he s, like S and Cl and, o a lesse ex en , Na and K, mos ly a he ims. The di e en
mine alogical composi ion be ween im and he co e g ains sugges s a o ma ion o e y small
c ys als o chlo ide and sulpha e du ing wea he ing.
Leaching es s on he same sample showed ha Cl and S a e he mos leachable, suppo ing he
hypo hesis o hei p esence a he im o he g ains, and no wi hin silica e glasses.
Also, he co e o he g ains is he e ogeneous: SEM-EDS obse a ions a highe esolu ion indica e
he coexis ence o se e al c ys als as silica es, oxides, ca bona es, me als inclusions and glass (Figu e
3.3.1.2). µ-XRF da a show a mo e de ailed dis ibu ion o he PTE han SEM-EDS esul s: his is
expec ed, as PTE a e gene ally below SEM-EDS analy ical esolu ion. Howe e , in ew cases when
he µ-XRF indica es a highe concen a ion o a gi en elemen , i is no possible o ind a coun e pa
in he SEM-EDS maps. Al hough he wo me hods analyse he same a eas, he de ec ed olume is
di e en : in µ-XRF he beam p obes a dep h o ew ens o mic ons, whe eas he SEM-EDS p obes
1-2 µm maximum. The PTE ich phase may no be p esen a he su ace o he g ain, so o be e ealed
by SEM-EDS, bu jus ew mic ons below, and de ec ed ins ead by µ-XRF.
Due o he spa ial esolu ion o acqui ed µ-XRF maps, lowe han ha o SEM-EDS, and he
he e ogeneous na u e o BA, a gi en µ-XRF analy ical pixel may sample a numbe o di e en
phases.
Th oughou he o e laps o single elemen s µ-XRF maps, he dis ibu ion o PTE was analysed and
associa ed o majo elemen s (Si, Ca, Mg, Na, e c) ob aining he mine alogical en i onmen in which
PTE a e inco po a ed. Among he PTE, Cu is p esen gene ally oge he wi h Na, K and Si, in glass
mo phologies obse ed wi h SEM-EDS. To no e, in he same a eas EDS analysis do no e ealed he
p esence o Cu-bea ing phases, indica ing ha Cu is below he ins umen al esolu ion o in iny
g ains unde he su ace. Cu was ound in one g ain as a Cu-Sn alloy also wi h Ni; Cu was also ound
as alloy/me al inclusions and d ople s dispe sed wi hin he glass as obse ed by Man o ani e al.
(Man o ani e al., 2021).
In a g ain, Ni occu s in alloys wi h Co and Mn, and wi h Co and C . Gene ally, howe e , Ni appea s
oge he wi h Fe and C , in a phase ha was con i med as ch omi e by XANES analysis, and, mos
93
equen ly, oge he wi h Na, K, Si and Al in an assemblage likely a glass. To no e, Ni was no ound
oge he wi h S and Cl.
Co was ound oge he wi h Ni, likely in alloy; o e lap wi h O indica es some deg ee o oxida ion. In
he same g ain, an o e lap o Co and Cl migh indica e o ma ion o chlo ides.
C is gene ally associa ed wi h Fe, bu also wi h Si, Ca, Fe, Na and K. The sugges ion is ha i is
dissol ed in a glass, o in iny ch omi e c ys als. C was no p esen oge he wi h S and Cl.
Pb is ound mos in la ge g ains, in he co e and in he ims o he g ains. I is associa ed wi h Ca and
Zn, bu no wi h Si. This could sugges a ca bona e phase. Pb occu s wi h S in ew g ains, whe e S is
p esen wi hin he co e. This is no unlikely, in iew o he s ong a ini y o Pb o sulphides. Pb is
also ound wi h Si, Na, K and Mg in Pb- ich glass.
Zn is ound in co e as ace in amo phous ma e ial and in ims, oge he wi h S and Cl sugges ing
hei p esence in sulpha es and chlo ides and oge he wi h Ti, in spinel-like s uc u e.
3.4 XANES
A majo ad an age o XAS is o be elemen speci ic, modelling he X- ay Abso p ion Edge o a gi en
elec on ansi ion o a gi en a omic species. I p o ides in o ma ion on he local en i onmen and
oxida ion s a e o he conside ed elemen , bu i does no p o ide a chemical in o ma ion o he
speci ic phase whe e he elemen is p esen . As he elemen may be in di e en oxida ion s a es and
di e en phases wi hin he a ea sampled by he beam, a decon olu ion o he di e en con ibu ions
is o en necessa y. Compa ing XANES esul s wi h hose om SEM-EDS and µ-XRF analysis, he
disad an age o no ha ing he composi ion o he emi ing phase, is compensa ed by he sensi i i y
o he XANES emission, able o p obe an elemen a ew ppm concen a ions and wi hin
submic ome ic phases. Oxida ion s a e and possible hos phases o each o he PTE a e he e
epo ed.
Cobal
XANES spec a we e eco ded a he Co K-edge in one clas , on which highe esolu ion SEM-EDS
analysis showed ha he g ain is made by a pa ially oxidized Co-Mn alloy, mingled wi h Al2O3 and
a Ca-silica e phase (Figu e 3.3.1.3).
XANES esul s con i m ha Co is p esen in a pa ially oxidized alloy: LCF analysis indica es ha
Co is p esen a 68(7)% in he o m o me al Co and a 32(4)% as Co-oxide. In he same g ain, a
single XRF spec um ex ac ed om he map highligh he p esence o also Ni, p esen below he
analy ical esolu ion o SEM-EDS. A XANES spec um collec ed a he Ni K-edge (labelled as
Ni3_1). indica es ha also Ni is p esen as a pa ially oxidized alloy: LCF esul s shows indeed ha
94
me al Ni [84(5)%] coexis s wi h di alen Ni-oxide [16(20)%]. He ea e , he label o he spec a will
be epo ed as Xa_b whe e X is he elemen , a is he a ea and b he poin analysed. (APPENDIX
XVI).
Figu e 3.3.1.3 Co-bea ing g ain. a) Image o he g ain aken wi h he mic ocame a a ailable a he XRF
beamline; b) SEM-BSE image on he same a ea wi h a h ee phases assemblage: me al cobal (whi e),
oxidized a ea wi h Co/Mn a io 2/1 (g ay) and mix u e o alumina and Ca-Al silica e (black); c) XRF
spec um ep esen a i e o he clas , wi h label o he main luo escence lines; d) No malized XANES
spec um collec ed on he same g ain a he Co K-edge.
Coppe
XANES spec a collec ed a he Cu K-edge in di e en clas s a e epo ed in Figu e 3.3.1.4. LCF
analysis (Table 3.3.1.3) sugges s ha Cu chemical en i onmen and oxida ion s a e a e he e ogeneous
e en in he same a ea, anging om me allic o Cu +II.
Th ee spec a (Cu1_1, Cu2_1 and Cu2_2) ha e a b oad whi e line peak a abou 8997 eV, oge he
wi h a mino p e-edge peaks a abou 8981 and 8985 eV, espec i ely. They i wi h di alen Cu-
oxide , bu he con ibu ion o mono alen Cu-oxide, and, in one spec um, o esidual me al, a e
necessa y o ob ain he bes i . In ano he g ain (Cu3_1) we ind a double a 8994 and 8998 eV,
possibly indica ing he p esence o cup ic ace a e.
SEM-EDS analysis on he same a eas did no show phases wi h su icien en ichmen in Cu o show
signi ican emission in Cu-Kα peaks. I is possible ha Cu in he a eas is below he analy ical
95
esolu ion o SEM-EDS, i.e. ew housands o ppm, bu i could be also an e ec o he di e en
sampling size o SEM-EDS and XANES analyses. Only in one case Cu was ound by SEM-EDS
analysis as well, in a Cu-Ni-Sn alloy (Figu e 3.3.1.2 c).
Figu e 3.3.1.4 No malized Cu XANES spec a o e e ence ma e ials ( op) and collec ed on a ious clas s o
he BA samples (bo om).
Compounds
Cu1 1
Cu2_1
Cu2_2
Cu3_1
Cu_T
Me al Cu
10 (4)
80 (3)
Cu2O
6 (4)
24 (5)
13 (4)
16 (4)
CuO
94 (2)
66 (3)
87 (3)
4 (2)
Cu(OH)2
11 (6)
Cu(CH3COO)2
89 (6)
Table 3.3.1.3 Resul s o he LCF analysis pe o med on he spec a collec ed a he Cu K-edge on BA clas s
( epo ed quan i ies a e %; sigmas in b acke s).
96
In his g ain, XANES spec um i s wi h me al Cu (Cu_T in Figu e 3.3.1.4), showing he ypical
iple a 8981, 8994 and 9004 eV, and indeed con i med by LCF esul s. The Cu specia ion in BA
showed ha Cu is p esen in di e en oxida ion s a es (0, +I and +II); his was also obse ed by
Rissle e al. (Rissle e al., 2020), and in e p e ed as an e ec o zones in he uel bed wi h di e en
access o he oxygen. He e, howe e , we obse e coexis ence o di e en oxida ion s a es wi hin he
same g ain.
Zinc
Zn was ound in BA in a numbe o di e en phases, some o hem well isible also in SEM-EDS.
Va ious XANES spec a (12 in o al) a he Zn K-edge we e collec ed on di e en clas s; a
selec ion o he mos ep esen a i e ones is epo ed in APPENDIX XI whe e is isible ha he
edge posi ion o all he spec a is simila and shi ed wi h espec o e e ence Zn oil, indica ing
ha Zn is no p esen as a me al bu mainly occu ed in oxida ion s a e +II (Table 3.3.1.4).
Clas Zn2_3 is he only one o ha e a weak p e-edge, whe eas wo peaks a abou 9665.3 and 9667.9
eV a e clea ly dis inguishable in all he spec a excep ha o clas Zn1_2, which has only one peak
a abou 9666.5 eV. The LCF p o ed di icul because o he he e ogenei y o he collec ed spec a.
In all he spec a, a g ea i is ob ained wi h Zn-ca bona e, in he o m o smi hsoni e (ZnCO3) o
hyd ozinci e (Zn5(CO3)2(OH)6). Smi hsoni e is he e i s obse ed, bu Zn in solid solu ion wi hin
ca bona e was epo ed by Pian one e al. (Pian one e al., 2004b) in an in es iga ion on wea he ing
phases. Hyd ozinci e was ound by Rissle e al. (Rissle e al., 2020) and dubiously by EXAFS
analysis by Tibe g e al. (Tibe g e al., 2021). Zinci e (ZnO) was ound in ew g ains, con i ming
SEM-EDS esul s and p e ious XAS da a by Rissle e al. (Rissle e al., 2020) and Tibe g e al.
(Tibe g e al., 2021).
Compounds
Zn1_1
Zn1_2
Zn1_3
Zn2_1
Zn2_2
Zn2_3
Zn3_1
Zn3_3
Zn3_4
Zn3_5
Zn3_6
ZnT
ZnO
29 (6)
32 (5)
36 (6)
28 (6)
ZnS
27 (3)
51 (3)
33 (3)
54 (2)
62 (2)
51 (2)
ZnCO3
15 (2)
45 (7)
39 (4)
44 (3)
28 (4)
21 (5)
64 (6)
ZnAl2O4
34 (3)
Zn4Si2O7(OH)2· (H2O)
41 (6)
17 (3)
9 (3)
24 (5)
Zn3(PO4)2
42 (4)
41 (5)
27 (10)
ZnFe2O4
34 (7)
43 (4)
Zn5(CO3)2(OH)6
31 (5)
34 (0.9)
26 (1)
22 (4)
29 (4)
29 (4)
26 (2)
ZnCl2
26 (10)
8 (2)
Table 3.3.1.4 Resul s o he LCF analysis pe o med on he spec a collec ed a he Zn K-edge on BA clas s
( epo ed quan i ies a e %; sigmas in b acke s).

97
Due o he simila i y o he XANES spec a o zinci e and Zn-hyd oxide, Zn(OH)2 could be also
p esen . In i e o he examined spec a he i equi ed he ZnS phase in subs an ial amoun . The
phase is he e i s obse ed, and could be p esen by educ ion o sulpha es du ing wea he ing. The
p esence o Zn-phospha e is no su p ising, as se e al Zn phospha e phases we e ound by (Pian one
e al., 2004b). Howe e , Zn-phospha e was no ound by Rissle e al. (Rissle e al., 2020). Also,
spinel phases like gahni e and Zn- e i e (ZnFe2O4) a e p esen , as well as he silica e hemimo phi e
[Zn4Si2O7(OH)2·H2O]. Bo h a e common indings in Rissle e al. (Rissle e al., 2020), and Tibe g
e al. (Tibe g e al., 2021). Howe e , a possible misin e p e a ion can be done due o he absence o a
s anda d o Zn in silica e glass, whe e i was ound he e and in Man o ani e al. (Man o ani e al.,
2021) (Table 3.3.1.5 2). Las , he ZnCl2 was ound only in one spec um (Zn2_1); his compound was
ound mainly in FA (Cai e al., 2015; Ki amu a e al., 2020) bu also in BA whe e i s p esence can be
explained by he encapsula ion o chlo ide wi hin sin e ed BA pa icles (Rissle e al., 2020). I is
possible ha Zn is dispe sed in small quan i ies, bu being a highly soluble sal , i s p esence poses
en i onmen al conce n.
Ch omium
The LCF analysis esul s showed ha h ee o he ou collec ed spec a (C 1_1, C 2_1, C 2_2) i
mainly wi h FeC 2O4, wi h a pe cen age anging om 60-77% (APPENDIX XIV and Figu e
3.3.1.5). In he spec a C 1_1 and C 2_1 was also ound me al C (23% and 27%, espec i ely) and
40% o C 2O3 in C 2_2. In one spec um (C 3_1) me al C (24%) and C 2O3 (76%) we e ound, in
ag eemen wi h SEM-EDS analy ical esul s o ch omium-aluminium oxide (C 1.81Al0.19O3). In all
XANES spec a C was p esen in he C 0 and C III+ oxida ion s a e. No e idence o C VI+, which
would show he ypical high in ensi y p e-edge peak a abou 5993 eV, was ound.
Lead
Se e al XANES spec a a he Pb L3-edge we e collec ed, which show he same ea u es and a e
almos iden ical: a e y b oad whi e line peak a 13052 eV is in a iably p esen (APPENDIX XII).
F om he compa ison o he edge posi ion wi h espec o Pb me al oil and Pb oxide s anda d
compound spec a, Pb is expec ed o be oxidized in all he clas s. The LCF analysis esul s showed
i s wi h PbCO3 (29-43%) and Pb3O4 (57-71%) (APPENDIX XV). In hese compounds, Pb is p esen
in +II and +III chemical o ms. O he e e ence compounds, like PbO, PbO2, and PbCl2 we e es ed,
bu none ga e a sa is ac o y i ing. Also, in he same a eas, S luo escence lines we e no de ec ed,
which disca ded PbS and PbSO4 as possible candida es. As o Zn, we did no y o i Pb in a glassy
en i onmen , so we canno ule ou he p esence o Pb in an alkali ich silica e glass, which could be
98
compa ible wi h he chemical composi ion o some o he in es iga ed clas s ( om XRF da a).
XANES spec a o Pb in PbO-Ga2O3 glasses show, simila ly o ou sample, a single b oad whi e line
peak, which is also simila o he XANES spec um o Pb in a silica e s uc u e (Choi e al., 1999;
Dub ail e al., 2009).
Nickel
Like Cu, Ni is ound in SEM-EDS only in he abo e desc ibed g ain oge he wi h Co, and is e ealed
jus by XRF. The XANES spec a a he Ni K-edge (APPENDIX XIII) we e compa ed wi h Ni me al
oil, NiO and Ni(OH)2.
LCF analysis shows ha Ni, like Cu and Co, is p esen in me al and oxidized o m, bu hyd a ion is
also possible. The esul s o LCF analysis (APPENDIX XVI) indica e ha he me al is always
pa ially oxidized and hyd a ed.
Figu e 3.3.1.5 No malized C XANES spec a o e e ence ma e ials ( op) and collec ed on a ious clas s o
he BA samples (bo om).
4. DISCUSSION
The a e o PTE
In p e ious in es iga ions on he specia ion o PTE, se e al po en ial hos mine als we e sugges ed
[11, 23, 56, 27, 29, 50–55]. This in es iga ion con i med he p e ious esul s, and possibly widened
somehow he lis (Table 3.3.1.5.1, 3.3.1.5.2, 3.3.1.5.3). Howe e , being silica e glasses he majo
99
phases o BA, a signi ican specia ion in he glassy phases can be expec ed. In BA, whe e local
equilib ia a e a ule, we may ind glasses wi h di e en composi ion, al hough gene ally en iched in
alkalies (Man o ani e al., 2021), able o hos he di e en a omic species in hei s uc u e. The glass
o med by he high empe a u e o he combus ion chambe is easily de ec ed in BSE images: i is
p esen in he co e o he g ains, i embeds he c ys als, and shows a composi ion o a Ca-Al silica e
en iched in alkalies. The same composi ional pa e n was shown by XRF, in a eas whe e SEM-BSE
images showed a glass. SEM-EDS analyses on he glass in he co e ound in ew g ains Zn, C o Pb
jus abo e de ec ion limi s, al hough e idence o PTE in silica e glasses was no con i med by
XANES. In BA se e al glassy phases coexis wi h di e en composi ion likely hos ing PTE. Because
o he lack o e e ence s anda ds o glass, XANES spec a migh miss he con ibu ion o PTE
p esen in glasses.
Mingling wi h c ys alline phases, and wi h a non-de ini e chemical composi ion, he cha ac e iza ion
o his he e ogeneous ma ix is a he complex ask. E en combining µ-XRF and SEM-EDS analysis,
only in ew g ains dis inc phases hos ing he in es iga ed PTE can be de ec ed. In p e ious
in es iga ions [23, 29], wi hou he use o µ-XRF, he XAS spec a we e always in e p e ed wi h
c ys alline phases s anda ds, o e looking possible con ibu ion o he glass. Bea ing his in mind we
may sugges a possible specia ion o each o he PTE.
Cu is ound in di e en oxida ion s a es. I was mainly ound in me al o ms, pu e o as an alloy,
which is pa ially oxidized as Cu I+ and Cu II+. I was obse ed as iny d ople s in he silica e glasses.
This wo k and Rissle e al. (Rissle e al., 2020) sugges ha i may also unde go wea he ing as a
hyd oxide o a chlo ide. Co is mos ly p esen as an alloy, whe e ound, wi h Mn, Ni o Fe, and only
pa ially oxidized o Co II+. XRF shows ha Pb, di e en ly om Cu, is dis ibu ed mainly in la ge
g ains, bo h in he co e and in he im, hos in glasses and ca bona e mine als in ag eemen wi h he
XANES esul s. Besides, in SEM in es iga ion, Pb was also ound as a Ca-plumba e phase possibly
o med by Pb- ich glass and lime. In a p e ious s udies on he specia ion o Pb in FA, i was ound
as me al Pb, PbCl2, PbO and PbCO3 (Zhu e al., 2018). C in highe concen a ion is gene ally ound
as an oxide, like spinel ch omi e o an Al-Fe-C oxide. In lowe concen a ion, C occu s in glasses.
No e idence o C VI+ o co ela ion wi h sulpha e was de ec ed. Ni is p esen as a me al o in spinel
solid solu ion oge he wi h C and Fe. Howe e , i looks mo e p one o al e a ion han C , o ming
Ni-bea ing oxides and hyd oxides.
Las , Zn is p esen in a numbe o phases, some o hem p obed by SEM-EDS, o he s mingled wi hin
a single 50x50µm2 a ea, iden i ied by XANES spec al decon olu ion. Zn is obse ed in silica es like
willemi e, ha dys oni e o hemimo phi e, in oxides and hyd oxides, like gahni e spinel and zinci e, in
ZnS, in he e y soluble o m o ZnCl2 and in ca bona es like smi hsoni e o hyd ozinci e ha can be
100
an al e a ion p oduc o hemimo phi e. Mo eo e , he p esence o Zn in a silica e glass is sugges ed
by a locally en ichmen e ealed by SEM-EDS. I was no ound in sulpha es o as a me al.
In Tables 5.1, 5.2, 5.3 a lis o he mine als con aining he in es iga ed PTE in BA in his wo k and
p e ious in es iga ions is epo ed. PTE we e ound in wo mine alogical occu ences, like i was
he e obse ed: as mino componen s in silica es, me als, oxides and hyd oxides, including glassy
phases, o as phases in hei own, as an e ec o hei local concen a ion. A u he di e ence is in
phases p esen as iny inclusions, well below 1 µm, which could be e ealed jus by XAS o TEM,
o , when in signi ican amoun , by XRD. An example is he Cu oxides inclusions, i.e. eno i e and
cup i e, which a e likely p esen o oxida ion o me al Cu, o ha o ZnCl2 and hemimo phi e,
obse ed only by XANES in his wo k and in Rissle e al. (Rissle e al., 2020). The nanoscopic
mine als show highe su ace and di e en size- ela ed p ope ies which should be aken ca e in any
geochemical modelling (Hochella e al., 2019). The p esence o PTE in submic ome ic c ys als o
glasses was e ealed by he XRF mapping, showing signi ican concen a ion o hem, in a eas whe e
hey we e no ound wi hin single phases by SEM.
Mo eo e , in he enclosed lis , se e al mine als appea jus in one single pape , like Zn2P2O7,
Zn3(PO4)2 · 4H2O o Zn2PO4(OH). These phases we e iden i ied by XRD, assumingly in signi ican
amoun , bu hey didn’ ind by o he au ho s. In Meima and Comans (Meima & Comans, 1999) as
much as 26% o he examined pa icles we e con aining Zn in me al o m, while he e in none o he
in es iga ed samples i was ound. Likewise, i was obse ed o Pb. This indica es ha each W E
plan has i s own mine alogy, and ha o any use o he BA, a speci ic in es iga ion should be done.
Howe e , om he lis i appea s ha compa ing wi h di e en W E plan s, we can see ha PTE a e
ound in some common mine alogic phases.
Fo Cu he commonly obse ed is in me al Cu, which is mo e o less al e ed as Cu I+ o Cu II+ oxides
o Cu(OH)2. The ca bona e o m, commonly obse ed in al e a ion o mining deposi s, is less
epo ed. In ew cases i may en e in he complex spinel oxide s uc u e. Cu associa ed in silica es
did no ind in his wo k, bu his was epo ed by Rissle a al. (Rissle e al., 2020) and Meima and
Comans (Meima & Comans, 1999). I p esen , Cu-silica es oge he wi h me al Cu a e p obably
combus ion p oduc s, while he o he s a e ela ed o subsequen wea he ing.
Zn is ound in a weal h o di e en phases. As a high empe a u e Zn dominan phase, zinci e is he
main mine al, bu also silica e willemi e and he spinels anklini e and gahni e a e commonly ound.
Zn-phospha es and me al Zn a e also ound, bu no in his in es iga ion. Zn is also p esen as an
impu i y in o he oxides, in silica e glasses, in eldspa s and py oxenes. The al e a ion p oduc s a e
silica e hyd a ed, hyd oxides, ca bona es and chlo ides. All o hem ha e been obse ed by XAS,
indica ing hei p esence as nanosized g ains. Such a he complex mine alogy o Zn p oduces an
107
Figu e 3.4.1: XRD pa e n collec ed o Piacenza samples (PC) and 0.063 – 0.2 samples Pa ma (PR) o
each ex ac ion.

108
Alam e al., 2021
≤ 0.125mm
Alam e al., 2021
0.125 - 1 mm
PC 0.2-0.3 mm
PR 0.063 - 0.2 mm
PR 0.3-0.5 mm
PR 2 - 4 mm
PR < 4 mm
Mine al
Chemical o mula
S0
S1
S2
S3
S4
S0
S1
S2
S3
S4
S0
S1
S2
S3
S4
S5
S0
S1
S2
S3
S4
S0
S1
S2
S3
S4
S0
S1
S2
S3
S4
S0
S1
S2
S3
S4
hali e
NaCl
x
x
x
x
x
x
x
gypsum
CaSO4 · 2H2O
x
x
e ingi e
Ca6Al2(SO4)3(OH)12 · 26H2O
x
x
hyd ocalumi e
Ca4Al2(OH)12(Cl,CO3,OH)2 · 4H2O
x
x
x
x
x
x
x
x
x
x
po landi e
Ca(OH)2
x
x
x
zeoli e
X(AlO2)n(SiO2)1-n · mH2O
x
x
calci e
CaCO3
x
x
x
x
x
x
x
x
x
x
x
x
x
apa i e
Ca5(PO4)3(Cl/F/OH)
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
anyd i e
CaSO4
x
x
x
x
x
la ni e
Ca2SiO4
x
x
x
x
spinel
XY2O4
x
x
x
x
x
x
x
x
x
magne i e
Fe2+Fe3+2O4
x
x
x
x
x
x
x
x
x
x
x
x
hema i e
Fe2O3
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
u ile
TiO2
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
co undum
Al2O3
x
x
x
x
x
x
Cu-Ti oxide
x
Pb-Fe oxide
x
wus i e
FeO
x
x
x
x
x
musco i e
KAl2(AlSi3O10)(OH)2
x
x
x
x
x
melili e
(Ca, Na)2(Mg, Fe, Al, Si)3O7
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
plagioclase
(Ca,Na)[Al(Al,Si)Si2O8]
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
py oxene
ABSi2O6
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
qua z
SiO2
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
Table 3.4.1: mine alogical phases ound (x) a e each ex ac ion in Alam e al. (2019), Piacenza BA and Pa ma BA
109
XRD analyses we e pe o med a he end o each s ep, and he esul s ob ained we e compa ed wi h
hose epo ed by Alam e al., 2019. X- ay di ac ion (Table 3.4.1) showed ha a e he i s s ep
hali e is emo ed in all samples; e ingi e, p esen in Piacenza and ound by Alam e al. (2019), and
po landi e, p esen only in Pa ma samples, a e emo ed a e ea men wi h ul apu e wa e . A e
he second s ep calci e and hyd ocalumi e a e no mo e p esen in all samples. Melili e is pa ially
emo ed in Alam e al., 2019, in his wo k Piacenza sample and in he 2 - 4 mm and bulk ≤4 mm
Pa ma samples. The dissolu ion o melili e is comple e in 0.063 - 0.2mm and 0.3 - 0.5mm Pa ma
g ain size melili e. A e he acid a ack, new mine alogical phases a e iden i ied, no mo e o e lapped
by he emo ed phases. In he Piacenza sample and in Pa ma smalle g ain size (0.063-0.2mm and
0.3-0.5) hema i e, magne i e and u ile a e iden i ied. In he Piacenza sample Cu-Ti and Pb-Fe oxides
we e also iden i ied, bu we e no ound a e he ex ac ion occu ed in he hi d s ep. A e he hi d
s ep melili e esidual is o ally emo ed and in Piacenza sample appea s co undum. In he ou h s ep
plagioclase in ensi y dec eases, indica ing he onse o a dissolu ion, and he e a e no signi ican
changes om he p e ious esidue. Only he Piacenza samples we e unde going o he i h s ep and,
a e a ack wi h HF and HClO4, only qua z, u ile and co undum a e p esen .
Figu e 3.4.2 Weigh loss in p og essi e ex ac ed ac ion. G een a eas co esponding a i s s ep (S1);
yellow a eas co esponding a second s ep (S2); ed a es co esponding a hi d s ep (S3); blue a eas
co esponding a ou h s ep (S4); g ey a es co esponding a esidues
110
In APPENDIX XVII he esul s o he XRF analyses o he bulk samples a he di e en s eps a e
epo ed. These esul s a e a e aged o 100% o he esidue; o ob ain he esidual amoun o each
oxide ( o majo elemen s), and a omic concen a ion ( o mino elemen s), he analy ical alue was
ecalcula ed by mul iplying he analy ical alue wi h he a io be ween he esidual alue and he one
be o e he SEP. Mo eo e , he concen a ions ob ained om he ou g ain size in he SEP om Pa ma
W E we e a e aged. As shown in igu e 3.4.2.3 we ha e o some elemen s like C and Fe, and, o a
mino amoun Ni, ha he co ec ed alue does no show a dec easing alue, i.e, he elemen s ays in
he esidual po ion, a leas wi hin he expe imen al unce ain y. O he elemen s, like S and Zn do
show a s ong dissolu ion du ing he s eps.
Figu e 3.4.3 Sequen ial ex ac ion o majo (a) and mino (b) elemen s. G een a eas co esponding a i s
s ep (S1); yellow a eas co esponding a second s ep (S2); ed a es co esponding a hi d s ep (S3); blue
a eas co esponding a ou h s ep (S4); g ey a es co esponding a esidues
The a e age o each elemen esidual a e he di e en s eps om he ou ac ions was used o
ob ain Figu e 3.4.3. The ac ion ex ac ed a e each s ep is ou lined o he majo and mino
elemen s. Al hough wi h he unce ain ies ela ed o possible sample in homogenei ies, we ind ha
Ba, C and Fe a e almos comple ely in he esiduals, whe eas Pb, Zn, LOI, S, Ca and S do show a
s ong dec ease a e he acid e ching. In he i s s ep B is almos comple ely ex ac ed, and Na and
K show a signi ican dec ease, sugges ing ha hey a e p esen in a highly soluble phase, like
chlo ides. This is obse ed o any g ain size, whe eas Zn and S (Figu e 3.4.4) con en dec ease in
he i s s ep only in he smalle g ain size, and o Pb he dec ease is jus obse ed in one g ain size.
A s ong dec ease o he esidual in he educing s age is obse ed mainly o Cu, indica ing possible
educ ion o hyd oxides and oxides o me al.
111
Figu e 3.4.4: Elemen s (mg/kg) in solid esidues om XRF da a
A he end o s ep 4, some elemen s a e almos comple ely leached, like S, Zn, S , Pb and Ca,
indica ing ha hey a e no concen a ed in esis an oxides, like spinels o in silica e c ys als o glass.
S ill, o hese elemen s a signi ican concen a ion o he elemen is p esen in he esidual, likely
indica ing hei p esence in a silica e phase, as willemi e o Zn- ich glass, o Zn, o in solu ion in
eldspa s o S (T ibaudino e al., 2005) O he elemen s like C and Ba a e concen a ed in he
esidual. Fo C his con i ms i s concen a ion in non-soluble oxides, whe eas o Ba he sugges ion
is ha he elemen is p esen in silica es, possibly in eldspa s. I is no clea whe he Ni has some
signi ican leaching.
112
4 CONCLUSIONS
The mine alogy, chemical composi ion and p ope ies o he BA in i e incine a o s in No he n I aly
we e examined. The a e age composi ion, and he changes o he composi ion wi h g ain size ollow
qui e simila ends in all he incine a o s. As shown in Figu e 3.2.1.3 o chap e 3.2 he majo and
mino elemen s composi ions a e e y close, and a e well g ouped in he composi ional a ia ion o
he incine a o s wo ldwide. This may indica e ha , in spi e o he di e en numbe s o was e inpu
be ween municipal and special was e, he inpu is compa able, a leas in he unbu ned ac ion. On
he o he side, as shown in Figu e 3.2.1.6 in chap e 3.2 he e a e o de s o magni ude in he leached
ac ion be ween he di e en incine a o s, wi h highe di e ences be ween he incine a o s o Fe a a
and Fo lì-Cesena, and he o he s. The di e ence is ela ed o he mine alogical composi ion, and o
whe e a gi en elemen occu s in a mo e soluble phase, and a ec s also whe he he ashes a e beyond
legisla ion limi s, as shown in chap e 3.4. The p esence o po landi e in Fe a a and Fo lì-Cesena
bu e s he pH o highe alues, o s abilise e ingi e, which does no dissol e wi h sulpha es. The
quan i a i e mine alogical di e ences (amo phous, ca bona es) ound be ween he W E plan s o
IREN and HERA g oups could be ela ed o di e en bu ning empe a u es, ope a ing p ocedu es o
wea he ing condi ions, and make an example on how he mine alogy may a ec he p ope ies o he
ashes.
The combined SEM-EDS, XRF-XANES, XRD analyses on di e en g ain size and di e en g ains
enabled o ind a numbe o new mine al hos s o he PTE (Co, Zn, Ni, Cu, Pb, C ), ound in me allic
inclusions, oxides, ca bona es, and amo phous ma ices. As such combined in es iga ion was no
p e iously done, we may assume ha he mine alogical a ie y which has since now been de e mined
in BA, al eady ep esen ed by a conside able numbe o phases, is jus a ac ion o he ac ual one.
As long as SEM-EDS is used on single g ains, we obse e ha each g ain shows chemically di e en
bulk composi ion, and mine alogical assemblages. Jus o an example Zn was ound in BA in 27
mine al phases, o which 15 we e con i med o disco e ed in his wo k. Also, wha is gene ally and
simply desc ibed as an amo phous o glassy phase, is in ac a numbe o di e en phases, each o
hem in local equilib ium wi h he embedded c ys als. This makes he p edic ion o he leaching
beha iou o he ashes a isky ask: he leached ac ion o PTE is jus a e y small ac ion, be ween
10-3 and 10-6 o he global con en o he elemen , and a sligh change in mine alogy, ha dly o no
de ec able by XRD, may ha e a p o ound e ec on he leaching o he samples. The p ecipi a ion o
a small amoun o a highly soluble phase con aining PTE may inc ease d ama ically he leached
ac ion.

113
We obse ed ha he mine al ac ion o BA is ex emely he e ogeneous, being made by slags, glass,
me allic componen s, each o hem chemically and mine alogically he e ogeneous; chemical and
mine alogical composi ional di e ences we e obse ed as a unc ion o g ain size, among di e en
slags and wi hin a single g ain. This comes om a combined e ec o he he e ogeneous inpu , bu
also o he empe a u e g adien s in he combus ion chambe , p omo ing di e en equilib ia a he
di e en empe a u es, and, las bu no leas , by he di e en wea he ing condi ions, like posi ion in
he pile, mois u e, di e en exposu e ime.
The e a e howe e some egula ea u es in he composi ional ela ions be ween he elemen s, which
could be ou lined by he analysis o di e en po ions o he same sample, so ed by g ain size. Two
opposi e ends a e obse ed: one shown by Si and g ain size, he o he , opposi e co ela ed o he
i s , is shown by Ca, Cl, S and he esidual loss on igni ion. The i s end is ollowed also by some
mo e li hophile elemen s, like Z and Rb, he la e likely p esen in eldspa o silica e glass. The
second end is ollowed by PTE elemen s like Cu and Zn, bu wi h some excep ions: in he W E om
Piacenza Zn does no ollow a speci ic end, and in he Fo lì-Cesena plan , Cu ollows he Si end.
Pb, Ni and C do no ollow nei he end, wi h he excep ion o he Fe a a W E, whe e Pb goes wi h
S. I appea s ha Cu and Zn a e hos ed in ca bona e, sulpha e o chlo ides in he di e en g ain size,
whe eas Pb, Ni, Co and C may ha e di e en hos mine als in he di e en composi ions. As o he
leaching beha iou i is gene ally obse ed ha leaching inc eases as he g ain size dec eases, o Cl
, Na (and K) and Cu, bu o he elemen s, like C and Ni ollow a di e en end in he W E plan s o
To ino, Piacenza and Pa ma, whe e hey ollow he end o Cl and Na, espec o Fe a a and Fo lì-
Cesena, whe e hey seem un ela ed o he g ain size. This again, highligh s he di e ence be ween
he di e en plan s.
Fo a possible ecycle o he BA, he esul s in leaching es s indica e ha all he g ain size below 2
mm, om any incine a o a e beyond legal limi s o some elemen . Chlo ine and Cu a e always
beyond legal limi s, and again we ind a di e ence be ween incine a o s: Ba, Ni, F a e abo e limi s
in he Fe a a and Fo lì-Cesena plan s, SO42- and C o he o he incine a o s. Ni and O he elemen s,
like Pb and Zn we e always leached below limi s, al hough in Fe a a he Pb leaching is close o he
c i ical alue.
The e o e, o make any use o he han as insula o ille s, some kind o ea men is needed. The
obse a ion ha PTE dec ease wi h inc easing g ain size, is no always co ec , and o Cu and Cl, in
he examined g ain size he leaching is so high ha i is no expec able ha simply sie ing he la ge
po ion will sol e he issue. Howe e , he la ge g ain size could be easie o wash, and he eac i i y
in he g ains could be slowe : ou SEP showed ha he leached ac ion, no ma e i s oxici y, is
highe in ine g ains. The highly eac i e na u e o he ashes can be used as an agg ega e in cemen ,
114
mos o highly ma u a ed ma e ial whe e cemen mine als a e p esen . Conc e e ob ained using BA
as agg ega e could ix he PTE in a s uc u e whe e leaching occu s less. By his espec an
in es iga ion on he pe o mance and on he leaching o conc e e, ob ained using ashes o di e en
g ain size as agg ega es in conc e e, be o e and a e washing could be p omising. Also, in ligh o
he obse ed di e ences in he mine alogy o he di e en incine a o s, we may expec di e en
pe o mances in conc e e using ashes om di e en plan s. P elimina y washing a some pH alue
should be use ul, as ou obse a ion showed ha mos o he coa se g ains do show a im, made by
smalle g ains, and likely he mo e eac i e pa . The washing should be made as o disagg ega e he
im po ion, whose sewage could be subjec o u he eco e y o me als.
Finally, a no e on he analysis o he ashes, conside ing as a geological ma e ial: gene ally speaking,
BA a e on a e age a ma e ial which can be chemically desc ibed wi hin he CaO-Al2O3-SiO2 sys em,
no a om he composi ion o basal ic ocks. The main di e ence is ha he a e age composi ion
comes om an a e age o mic o o submic ome ic equilib ia, occu ing wi hin each g ain.
Equilib ium is no always achie ed, and wea he ing plays a majo ole. To p edic he he modynamic
beha iou would equi e p elimina y homogeniza ion, which is no economically easible, and
he e o e he p edic ions on he a e o he incine a ed ma e ial a e a isky ask. Howe e a weal h o
in o ma ion is e ained in he g ains size eac ions, which in ol e he empe a u e and he modynamic
condi ions o he eac ions in he incine a o , whose knowledge could allow o be e cons ain he
ope a ing condi ions, o minimise he pa icle leaching and ob ain a mo e sui able ma e ial o highe
alue uses.
115
REFERENCES
Ab amo , S., He, J., Wimme , D., Lemloh, M. L., Muehe, E. M., Gann, B., Roehm, E., Ki chho , R.,
Babechuk, M. G., Schoenbe g, R., Tho wa h, H., Helle, T., & Kapple , A. (2018). Hea y me al
mobili y and aluable con en s o p ocessed municipal solid was e incine a ion esidues om
Sou hwes e n Ge many. Was e Managemen , 79, 735–743.
h ps://doi.o g/10.1016/j.wasman.2018.08.010
Alam Q, Laza o A, Schollbach K, B ouwe s HJH (2020a) Chemical specia ion, dis ibu ion and
leaching beha io o chlo ides om municipal solid was e incine a ion bo om ash. Chemosphe e,
241:124985. h ps://doi.o g/10.1016/j.chemosphe e.2019.124985
Alam Q, Laza o A, Schollbach K, B ouwe s HJH (2020b) Chemical specia ion, dis ibu ion and
leaching beha io o chlo ides om municipal solid was e incine a ion bo om ash. Chemosphe e,
241:124985. h ps://doi.o g/10.1016/j.chemosphe e.2019.124985
Alam, Q., Schollbach, K., an Hoek, C., an de Laan, S., de Wol , T., & B ouwe s, H. J. H. (2019).
In-dep h mine alogical quan i ica ion o MSWI bo om ash phases and hei associa ion wi h
po en ially oxic elemen s. Was e Managemen , 87, 1–12.
h ps://doi.o g/10.1016/j.wasman.2019.01.031
Akinyemi, S. A., Gi a i, W. M., Thobakgale, R., Pe ik, L. F., Nyakuma, B. B., Howe , J. C., & Sil a,
L. F. O. (2020). Geochemical ac iona ion o haza dous elemen s in esh and d illed wea he ed
Sou h A ican coal ly ashes. En i onmen al geochemis y and heal h, 42, 2771-2788.
ANPA Agenzia Nazionale pe la P o ezione dell’Ambien e (2002). Il nuo o elenco dei i iu i e gli
schemi di asposizione. www.anpa.i
As up, T., Mun oni, A., Pole ini, A., Pomi, R., Van Ge en, T., & Van Zome en, A. (2016).
T ea men and euse o incine a ion bo om ash. En i onmen al Ma e ials and Was e, 607-645.
Academic P ess. h ps://doi.o g/10.1016/B978-0-12-803837-6.00024-X
Assi, A., Bilo, F., Fede ici, S., Zacco, A., Depe o, L. E., & Bon empi, E. (2020). Bo om ash de i ed
om municipal solid was e and sewage sludge co-incine a ion: Fi s esul s abou cha ac e iza ion
and euse. Was e Managemen , 116, 147–156. h ps://doi.o g/10.1016/j.wasman.2020.07.031
Ba one G, Caggiani MC, Cocca o A, Finocchia o C, Fugazzo o M, Lanza ame G, e al.(2020)
Geopolyme p oduc ion o conse a ion- es o a ion using Sicilian aw ma e ials: easibili y s udies.
IOP Con e ence Se ies: Ma e ials Science and Enginee ing, 777:012001.
h ps://doi.o g/10.1088/1757-899X/777/1/012001
Bawab J, Kha ib J, Kenai S, Sonebi M. (2021). A Re iew on Cemen i ious Ma e ials Including
Municipal Solid Was e Incine a ion Bo om Ash (MSWI-BA) as Agg ega es. Buildings, 11(5), 179.
h ps://doi.o g/10.3390/buildings11050179
Bayuseno AP, Schmahl WW (2011). Cha ac e iza ion o MSWI ly ash h ough mine alogy and wa e
ex ac ion. Resou ces, Conse a ion and Recycling. 55 (5), 524–534.
h ps://doi.o g/10.1016/j. escon ec.2011.01.002
Bayuseno, A. P., & Schmahl, W. W. (2010). Unde s anding he chemical and mine alogical p ope ies
o he ino ganic po ion o MSWI bo om ash. Was e Managemen , 30(8–9), 1509–1520.
h ps://doi.o g/10.1016/j.wasman.2010.03.010
116
Be olini, L., Ca sana, M., Cassago, D., Cu zio, A. Q., & Collepa di, M. (2004). MSWI ashes as
mine al addi ions in conc e e. Cemen and Conc e e Resea ch. 34(10), 1899–1906.
h ps://doi.o g/10.1016/j.cemcon es.2004.02.001
Bou salas, A., Vandepe e, L. J., G imes, S. M., Themelis, N., & Cheeseman, C. R. (2015).
P oduc ion o py oxene ce amics om he ine ac ion o incine a o bo om ash. Was e
Managemen . 45, 217-225. h ps://doi.o g/10.1016/j.wasman.2015.02.016
B unne , P. H., & Rechbe ge , H. (2015). Was e o ene gy - key elemen o sus ainable was e
managemen . Was e Managemen . 37, 3–12. h ps://doi.o g/10.1016/j.wasman.2014.02.003
Cai, X., Huang, Q. xing, Alhadj-Mallah, M. mallaye, Chi, Y., & Yan, J. hua. (2015). Cha ac e iza ion
o zinc apo condensa ion in ly ash pa icles using synch o on X- ay abso p ion spec oscopy.
Jou nal o Zhejiang Uni e si y: Science A. 16(1), 70–80. h ps://doi.o g/10.1631/jzus.A1400178
Ca iglia C., Des e anis E., Be nasconi D., e al (2020) En i onmen al managing o bo om ashes om
municipal he mo alo iza ion was e o ci il applica ions, as a unc ion o pa icle size, based on
s eam washing. In: EGU Gene al Assembly Con e ence Abs ac s . p 17649
Ca iglia, C., Con alonie i, G., Co azza i, I., Des e anis, E., Mand one, G., Pas e o, L., Boe o, R., &
Pa ese, A. (2019). E ec s o pa icle size on p ope ies and he mal ine iza ion o bo om ashes
(MSW o Tu in’s incine a o ). Was e Managemen . 84, 340–354.
h ps://doi.o g/10.1016/j.wasman.2018.11.050
CEWEP. (2016). Bo om Ash Fac Shee . h ps://www.cewep.eu/bo om-ash- ac shee / (Accessed 20
Oc 2021)
Chandle , A. J., Eighmy, T. T., Hjelma , O., Kosson, D. S., Sawell, S. E., Vehlow, J., & Ha lén, J.
(1997). Municipal solid was e incine a o esidues. Else ie .
Chen, C. H., & Chiou, J. (2007). Dis ibu ion o chlo ide ion in MSWI bo om ash and de-chlo ina ion
pe o mance. Jou nal o Haza dous Ma e ials. 148(1-2), 346-352.
h ps://doi.o g/10.1016/j.jhazma .2007.02.046
Chen, H., Lin, H., Zhang, P., Yu, L., Chen, L., Huang, X., & Li, D. (2021). Immobilisa ion o hea y
me als in haza dous was e incine a ion esidue using SiO2–Al2O3–Fe2O3–CaO glass-
ce amic. Ce amics In e na ional. 47(6), 8468-8477. h ps://doi.o g/10.1016/j.ce amin .2020.11.213
Chimenos, J. M.; Fe nandez, A. I.; Mi alles, L.; Sega a, M.; & Espiell, F. (2003) Sho - e m na u al
wea he ing o MSWI bo om ash as a unc ion o pa icle size. Was e Managemen . 23(10), 887-895.
h ps://doi.o g/10.1016/S0956-053X(03)00074-6
Chimenos JM, Sega a M, Fe nández MA, Espiell F (1999) Cha ac e iza ion o he bo om ash in
municipal solid was e incine a o . Jou nal o Haza dous Ma e ials. 64:211–222.
h ps://doi.o g/10.1016/S0304-3894(98)00246-5
Choi, Y. G., Kim, K. H., Che no , V. A., & Heo, J. (1999). Pb LIII-edge EXAFS and XANES
analyses on he s uc u al en i onmen o lead in PbO-Ga2O3 glasses. Jou nal o Non-C ys alline
Solids. 246(1), 128–135. h ps://doi.o g/10.1016/S0022-3093(99)00010-1
Commission o Eu opean Communi ies. Towa ds a Ci cula Economy: A Ze o Was e P og amme o
Eu ope; Communica ion No. 398; (COM (2014), 398); Commission o Eu opean Communi ies:
123
Olsson, S., Gus a sson, J. P., Be gg en Kleja, D., Bendz, D., & Pe sson, I. (2009). Me al leaching
om MSWI bo om ash as a ec ed by sal o dissol ed o ganic ma e . Was e Managemen . 29(2),
506–512. h ps://doi.o g/10.1016/j.wasman.2008.03.017
Ox o d Ins umen s, (2006). INCA.
Pan J.R., Huang C, Kuo J.J., Lin S.H. (2008) Recycling MSWI bo om and ly ash as aw ma e ials
o Po land cemen . Was e Managemen . 28:1113–1118.
h ps://doi.o g/10.1016/j.wasman.2007.04.009
Pagani, A., F ancescon, F., Pa ese, A., & Diella, V. (2010). Sani a y-wa e i eous body
cha ac e iza ion me hod by op ical mic oscopy, elemen al maps, image p ocessing and X- ay powde
di ac ion. Jou nal o he Eu opean Ce amic Socie y. 30(6), 1267–1275.
h ps://doi.o g/10.1016/j.jeu ce amsoc.2009.11.008
Palomo A, Mal se a O, Ga cia-Lodei o I, Fe nández-Jiménez A. (2021). Po land Ve sus Alkaline
Cemen : Con inui y o Clean B eak: “A Key Decision o Global Sus ainabili y.” F on ie s in
Chemis y. 9:11. h ps://doi.o g/10.3389/ chem.2021.705475
Pé ez-Ma ínez, S., Gi o-Paloma, J., Maldonado-Alameda, A., Fo mosa, J., Que al , I., & Chimenos,
J. M. (2019). Cha ac e isa ion and pa i ion o aluable me als om WEEE in wea he ed municipal
solid was e incine a ion bo om ash, wi h a iew o eco e ing. Jou nal o Cleane P oduc ion. 218,
61–68. h ps://doi.o g/10.1016/j.jclep o.2019.01.313
Pe ugini, D.; De Campos, C.P.; E el-Ing isch, W.; Dingwell, D.B. (2012).The space and ime
complexi y o chao ic mixing o silica e mel s: Implica ions o igneous pe ology. Li hos. 155, 326–
340. h ps://doi.o g/10.1016/j.li hos.2012.09.010
Pian one, P., Bodénan, F., & Cha ele -Snida o, L. (2004a). Mine alogical s udy o seconda y mine al
phases om wea he ed MSWI bo om ash: Implica ions o he modelling and apping o hea y
me als. Applied Geochemis y. 19(12), 1891–1904. h ps://doi.o g/10.1016/j.apgeochem.2004.05.006
Pian one, P., Bodénan, F., & Cha ele -Snida o, L. (2004b). Mine alogical s udy o seconda y mine al
phases om wea he ed MSWI bo om ash: Implica ions o he modelling and apping o hea y
me als. Applied Geochemis y. 19(12), 1891–1904. h ps://doi.o g/10.1016/j.apgeochem.2004.05.006
Pos , J. E., & Bish, D. L. (1989). Rie eld e inemen o c ys al s uc u es using powde X- ay
di ac ion da a. Mode n powde di ac ion. 20, 277-308. h ps://doi.o g/10.1515/9781501509018
Pshinko, G. N., Koso uko , A. A., Puzy naya, L. N., & Kobe s, S. A. (2013). Reco e y o U(VI)
om aqueous media wi h laye ed double hyd oxides o Zn and Al, in e cala ed wi h complexones.
Radiochemis y. 55(6), 601–604. h ps://doi.o g/10.1134/S1066362213060064
Qiu, Q., Jiang, X., L , G., Chen, Z., Lu, S., Ni, M., ... & Deng, X. (2018). Adso p ion o hea y me al
ions using zeoli e ma e ials o municipal solid was e incine a ion ly ash modi ied by mic owa e-
assis ed hyd o he mal ea men . Powde Technology. 335, 156-163.
h ps://doi.o g/10.1016/j.pow ec.2018.05.003
Rankin, G. ~A. (1915).The e na y sys em CaO-Al 2 O 3 -SiO 2 , wi h op ical s udy by F. E. W igh .
Am. J. Sci., 39, 1–79. h ps://doi.o g/10.2475/ajs.s4-39.229.1
Rau e , G., López-Sánchez, J. F., Sahuquillo, A., Rubio, R., Da idson, C., U e, A., & Que au ille ,
P. (1999). Imp o emen o he BCR h ee s ep sequen ial ex ac ion p ocedu e p io o he

124
ce i ica ion o new sedimen and soil e e ence ma e ials. Jou nal o En i onmen al Moni o ing.
1(1), 57–61. h ps://doi.o g/10.1039/a807854h
Ra el, B., & New ille, M. (2005). ATHENA, ARTEMIS, HEPHAESTUS: Da a analysis o X- ay
abso p ion spec oscopy using IFEFFIT. Jou nal o Synch o on Radia ion. 12(4), 537–541.
h ps://doi.o g/10.1107/S0909049505012719
Rie eld, H. M. (1967). Line p o iles o neu on powde -di ac ion peaks o s uc u e
e inemen . Ac a C ys allog aphica. 22(1), 151-152. h ps://doi.o g/10.1107/S0365110X67000234
Rissle , J., Klemen ie , K., Dahl, J., S eena i, B. M., & Edo, M. (2020). Iden i ica ion and
Quan i ica ion o Chemical Fo ms o Cu and Zn in MSWI Ashes Using XANES. Ene gy and Fuels.
34(11), 14505–14514. h ps://doi.o g/10.1021/acs.ene gy uels.0c02226
Rungche A, Poon CS, Chindap asi P, Pim aksa K. (2017). Syn hesis o low- empe a u e calcium
sul oalumina e-beli e cemen s om indus ial was es and hei hyd a ion: Compa a i e s udies
be ween ligni e ly ash and bo om ash. Cemen and Conc e e Composi ies. 83:10–19.
h ps://doi.o g/10.1016/j.cemconcomp.2017.06.013
San os, R. M., Me ens, G., Salman, M., Cize , Ö., & Van Ge en, T. (2013). Compa a i e s udy o
ageing, hea ea men and accele a ed ca bona ion o s abiliza ion o municipal solid was e
incine a ion bo om ash in iew o educing egula ed hea y me al/me alloid leaching. Jou nal o
En i onmen al Managemen . 128, 807-821. h ps://doi.o g/10.1016/j.jen man.2013.06.033
Sen hama ai, R. M., & Manoha an, P. D. (2005). Conc e e wi h ce amic was e agg ega e. Cemen
and Conc e e Composi es. 27(9-10), 910-913 h ps://doi.o g/10.1016/j.cemconcomp.2005.04.003
Se oodeh Jah omy, S., Jo dan, C., Azam, M., We ne , A., Ha asek, M., & Win e , F. (2019). Fly
ash om municipal solid was e incine a ion as a po en ial he mochemical ene gy s o age ma e ial.
Ene gy & Fuels. 33(7), 5810-5819. h ps://doi.o g/10.1021/acs.ene gy uels.8b04106
Sha ma, A., & Yoo, S. I. (2018). Subsolidus phase ela ionships in he Al2O3–SnO2–ZnO e na y
sys em a 1200° C in ai . Jou nal o Alloys and Compounds. 740, 536-540.
h ps://doi.o g/10.1016/j.jallcom.2017.10.160
She chenko, M., Jak, E. (2019). Expe imen al Liquidus S udy o he Te na y CaO-ZnO-SiO2
Sys em. Me allallu gical and Ma e ials T ansi ion B. 50, 2780–2793.
h ps://doi.o g/10.1007/s11663-019-01709-7
Song, Y., Li, J., Peng, M., Deng, Z., Yang, J., Liu, W., Shi, Z., & Lin, Z. (2019). Iden i ica ion o
C (VI) specia ion in e ous sul a e- educed ch omi e o e p ocessing esidue ( COPR) and impac s
o en i onmen al ac o s e osion on C (VI) leaching. Jou nal o Haza dous Ma e ials. 373(Ma ch),
389–396. h ps://doi.o g/10.1016/j.jhazma .2019.03.097
Speise , C.; Baumann, T.; Niessne , R. (2001). Cha ac e iza ion o municipal solid was e incine a ion
(MSWI) bo om ash by scanning elec on mic oscopy and quan i a i e ene gy dispe si e X- ay
mic oanalysis (SEM/EDX). F esenius. Jou nal o En i onmen al Analy ical. Chemis y. 370, 752–
759, h ps://doi.o g/10.1007/s002160000659
S eena i, B.-M., & No én, K. (2008). Specia ion o Zinc in ash in es iga ed by X- ay abso p ion
spec oscopy. 50.
125
S e en, W. (2021). In oducing he An h opocene: The human epoch: This a icle belongs o Ambio’s
50 h Anni e sa y Collec ion. Theme: An h opocene. Ambio, 50(10), 1784–1787.
h ps://doi.o g/10.1007/s13280-020-01489-4
Suá ez-Macías, J., Te ones-Sae a, J. M., Iglesias-Godino, F. J., & Co pas-Iglesias, F. A. (2021).
E alua ion o physical, chemical, and en i onmen al p ope ies o biomass bo om ash o use as a
ille in bi uminous mix u es. Sus ainabili y, 13(8), 4119. h ps://doi.o g/10.3390/su13084119
Suzuki, R. O., Naga a, J. I., & Risold, D. (1998). Expe imen al Phase Equilib ia in he PbOx‐CaO
Sys em. Jou nal o he Ame ican Ce amic Socie y. 81(9), 2493-2496. h ps://doi.o g/10.1111/j.1151-
2916.1998. b02651.x
Šyc, M., Simon, F. G., Hykš, J., B aga, R., Biganzoli, L., Cos a, G., Funa i, V., & G osso, M. (2020).
Me al eco e y om incine a ion bo om ash: S a e-o - he-a and ecen de elopmen s. Jou nal o
Haza dous Ma e ials. Vol. 393. Else ie B.V. h ps://doi.o g/10.1016/j.jhazma .2020.122433
Šyc, M., K auso á, A., Kameníko á, P., Šomplák, R., Pa las, M., Zach, B., & Punčochář, M. (2018).
Ma e ial analysis o Bo om ash om was e- o-ene gy plan s. Was e Managemen . 73, 360-366.
h ps://doi.o g/10.1016/j.wasman.2017.10.045
Tang, P., Flo ea, M. V. A., Spiesz, P., & B ouwe s, H. J. H. (2015). Cha ac e is ics and applica ion
po en ial o municipal solid was e incine a ion (MSWI) bo om ashes om wo was e- o-ene gy
plan s. Cons uc ion and Building Ma e ials. 83, 77–94.
h ps://doi.o g/10.1016/j.conbuildma .2015.02.033
Tibe g, C., Sjös ed , C., & Ka l eld Fedje, K. (2021). Specia ion o Cu and Zn in bo om ash om
solid was e incine a ion s udied by XAS, XRD, and geochemical modelling. Was e Managemen .
119, 389–398. h ps://doi.o g/10.1016/j.wasman.2020.10.023
Toby, B. H., & Von D eele, R. (2013). GSAS-II: he genesis o a mode n open-sou ce all pu pose
c ys allog aphy so wa e package. Jou nal o Applied C ys allog aphy. 46, 544–549.
h ps://doi.o g/h ps://doi.o g/10.1107/S0021889813003531
Tolle S, Funa i V, Vasumini I, Dinelli E. (2021). Geochemical cha ac e iza ion o su ace sedimen s
om he Rid acoli ese oi a ea and su oundings, I aly. De ails on bulk composi ion and g ain size.
Jou nal o Geochemical Explo a ion. 231:106863. h ps://doi.o g/10.1016/J.GEXPLO.2021.106863
Tong, L., He, J., Wang, F., Wang, Y., Wang, L., Tsang, D. C. W., Hu, Q., Hu, B., & Tang, Y. (2020).
E alua ion o he BCR sequen ial ex ac ion scheme o ace me al ac iona ion o alkaline
municipal solid was e incine a ion ly ash. Chemosphe e. 249, 126115.
h ps://doi.o g/10.1016/j.chemosphe e.2020.126115
T ibaudino, M., Benna, P., Nes ola, F., Meneghini, C., & B uno, E. (2005). The modynamic
beha iou o he high- empe a u e P1-I1 phase ansi ion along he CaAl2Si2O8 -S Al2Si208 join.
Physics and Chemis y o Mine als. 32(4), 314–321. h ps://doi.o g/10.1007/s00269-005-0469-4
T i uno ic P.D., Ma inko ic S.R., Tokalic R.D., Ma ijase ic S.D. (2010). The e ec o he con en
o unbu ned ca bon in bo om ash on i s applicabili y o oad cons uc ion. The mochimca Ac a.
498:1–6. h ps://doi.o g/10.1016/j. ca.2009.10.022
T ischle , H. (2016). The An h opocene: A Challenge o he His o y o Science, Technology, and
he En i onmen . In e na ional Jou nal o His o y and E hics o Na u al Sciences, Technology and
Medicine. 24(3), 309–335. h ps://doi.o g/10.1007/s00048-016-0146-3
126
Ty e , M. (2013). Municipal solid was e incine a o (MSWI) conc e e. Eco-e icien conc e e. 273-
310. Woodhead Publishing. h ps://doi.o g/10.1533/9780857098993.3.273
Tzanakos K, Mimilidou A, Anas asiadou K, S a akis A, Gida akos E. (2014).
Solidi ica ion/s abiliza ion o ash om medical was e incine a ion in o geopolyme s. Was e
Managemen . 34:1823–8. h ps://doi.o g/10.1016/j.wasman.2014.03.021.
Wang, S. J., He, P. J., Shao, L. M., & Zhang, H. (2016). Mul i unc ional e ec o Al2O3, SiO2 and
CaO on he ola iliza ion o PbO and PbCl2 du ing was e he mal ea men . Chemosphe e. 161, 242-
250. h ps://doi.o g/10.1016/j.chemosphe e.2016.07.020
Wei, Y., Mei, X., Shi, D., Liu, G., Li, L., & Shimaoka, T. (2017). Sepa a ion and cha ac e iza ion o
magne ic ac ions om was e- o-ene gy bo om ash wi h an emphasis on he leachabili y o hea y
me als. En i onmen al Science and Pollu ion Resea ch. 24(17), 14970–14979.
h ps://doi.o g/10.1007/s11356-017-9145-8
Wei, Y., Shimaoka, T., Sa a zadeh, A., & Takahashi, F. (2011a). Mine alogical cha ac e iza ion o
municipal solid was e incine a ion bo om ash wi h an emphasis on hea y me al-bea ing phases.
Jou nal o Haza dous Ma e ials. 187(1–3), 534–543. h ps://doi.o g/10.1016/j.jhazma .2011.01.070
Wei Y, Shimaoka T., Sa a zadeh A., Takahashi F. (2011b). Al e a ion o municipal solid was e
incine a ion bo om ash ocusing on he e olu ion o i on- ich cons i uen s. Was e Managemen .
31:1992–2000. h ps://doi.o g/10.1016/j.wasman.2011.04.021
Wei Y, Shimaoka T., Sa a zadeh A., Takahashi F. (2011c). Mine alogical cha ac e iza ion o
municipal solid was e incine a ion bo om ash wi h an emphasis on hea y me al-bea ing phases.
Jou nal o Haza dous Ma e ials. 187:534–543. h ps://doi.o g/10.1016/j.jhazma .2011.01.070
Wiles, C.C. (1996). Municipal solid was e combus ion ash: S a e-o - he-knowledge. Jou nal o
Haza dous Ma e ials. 47, 325–344, h ps://doi.o g/10.1016/0304-3894(95)00120-4
Winne eld F., Lo henbach B. (2010). Hyd a ion o calcium sul oalumina e cemen s - Expe imen al
indings and he modynamic modelling. Cemen and Conc e e Resea ch. 40:1239–1247.
h ps://doi.o g/10.1016/j.cemcon es.2009.08.014
W obel, P. M., Bogo ac, M., Sghaie , H., Leani, J. J., Miglio i, A., Padilla-Al a ez, R., Czyzycki,
M., Osan, J., Kaise , R. B., & Ka ydas, A. G. (2016). LabVIEW in e ace wi h Tango con ol sys em
o a mul i- echnique X- ay spec ome y IAEA beamline end-s a ion a Ele a Sinc o one T ies e.
Nuclea Ins umen s and Me hods in Physics Resea ch. Sec ion A: Accele a o s, Spec ome e s,
De ec o s and Associa ed Equipmen , 833, 105–109. h ps://doi.o g/10.1016/j.nima.2016.07.030
Yang, Y., Wang, Z. M., Liu, C., & Guo, X. C. (2012). Enhanced P, N and C emo al om domes ic
was ewa e using cons uc ed we land employing cons uc ion solid was e (CSW) as main subs a e.
Wa e Science and Technology. 66(5), 1022-1028. h ps://doi.o g/10.2166/ws .2012.277
Yao, J., Li, W. B., Kong, Q., Xia, F., & Shen, D. S. (2012). E ec o wea he ing on he mobili y o
zinc in municipal solid was e incine a o bo om ash. Fuel. 93, 99–104.
h ps://doi.o g/10.1016/j. uel.2011.11.026
Zalasiewicz, J., Williams, M., Fo ey, R., Smi h, A., Ba y, T. L., Coe, A. L., Bown, P. R., Rawson,
P. F., Gale, A., Gibba d, P., G ego y, F. J., Hounslow, M. W., Ke , A. C., Pea son, P., Knox, R.,
Powel, J., Wa e s, C., Ma shall, J., Oa es, M., & S one, P. (2011). S a ig aphy o he an h opocene.
127
Philosophical T ansac ions o he Royal Socie y A: Ma hema ical, Physical and Enginee ing
Sciences. 369(1938), 1036–1055. h ps://doi.o g/10.1098/ s a.2010.0315
Zanelli, C., Con e, S., Molina i, C., Solda i, R., & Dondi, M. (2021). Was e ecycling in ce amic iles:
a echnological ou look. Resou ces, Conse a ion and Recycling. Vol. 168. Else ie B.V.
h ps://doi.o g/10.1016/j. escon ec.2020.105289
Ze enbe gen, C., Van Reeuwijk, L. P., B adley, J. P., Comans, R. N. J., & Schuiling, R. D. (1998).
Wea he ing o MSWI bo om ash wi h emphasis on he glassy cons i uen s. Jou nal o geochemical
explo a ion. 62(1-3), 293-298. h ps://doi.o g/10.1016/S0375-6742(97)00033-2
Zhan, X., Hu, C., Gong, J., Xu, T., Li, J., Yang, L., & Zhong, S. (2018). Co-disposal o MSWI ly
ash and elec oly ic manganese esidue based on geopolyme ic sys em. Was e Managemen . 82, 62-
70. h ps://doi.o g/10.1016/j.wasman.2018.10.014.
Zhu, F., Xiong, Y., Wang, Y., Wei, X., Zhu, X., & Yan, F. (2018). Hea y me al beha io in
“Washing-Calcina ion-Changing wi h Bo om Ash” sys em o Recycling o Fou Types o Fly
Ashes. Was e Managemen . 75, 215–225. h ps://doi.o g/10.1016/j.wasman.2018.01.032
WEB REFERENCES
Dimond, h ps://www.diamond.ac.uk/Public/How-we-wo k/How-Diamond-Wo ks.h ml , consul ed in
25/10/2022.
Na ional Ins i u e o S anda ds and Technology,
h ps://physics.nis .go /PhysRe Da a/X ayMassCoe /ElemTab/z82.h ml , consul ed in 26/11/2022.
RJL Mic o & Analy ic, h ps://www. jl-mic oanaly ic.de/en/sem-edx- em-edx-analyse/sem-edx-de ek o en-
se-be-edx/ , consul ed in 11/11/2022.
U. S. Ene gy In o ma ion Adminis a ion, Biomass Explained – Was e- o-Ene gy (Municipal Solid Was e),
h ps://www.eia.go /ene gyexplained/biomass/was e- o-ene gy-in-dep h.php , consul ed in 25/10/2022.
Wikimedia Commons,
h ps://commons.wikimedia.o g/wiki/File:XANES_spec um_Fe_XAS_Ca pen e _2010.png , consul ed in
30/11/2022.
128
APPENDIX I
Linea Pea son’s (lowe iangle) and Spea man’s p ank co ela ion (uppe iangle) o
e alua ing co ela ion g ade be ween elemen s and he g ain size (log10) o
a)
his wo k and o
hose o
b)
Ca iglia e al. (2019) and
c)
Logino a e al. (2019). Co ela ion able o < 2mm g ain
size wi h majo elemen s a e also epo ed
(d)
. Pea son’s ep esen s he linea co ela ion. =
0 no co ela ion. = 1 comple ely co ela ed. while Spea man’s ank is signi ican (co ela ed)
i p < 0.05.
a) Da a om his wo k
Log(10)
size
Si
Ca
Fe
Al
Na
Mg
Ti
K
P
Mn
LOI
S
C
Cu
Ni
Zn
Pb
S
Cl
Ba
Z
Rb
Log(10)
size
0.000
0.000
0.107
0.518
0.007
0.072
0.017
0.189
0.185
0.627
0.000
0.000
0.535
0.005
0.786
0.000
0.277
0.094
0.000
0.003
0.000
0.000
Si
0.954
-
0.000
0.207
0.628
0.001
0.063
0.003
0.306
0.077
0.582
0.000
0.000
0.470
0.014
0.976
0.003
0.362
0.067
0.000
0.002
0.000
0.000
Ca
-0.936
-0.992
-
0.152
0.484
0.002
0.030
0.008
0.214
0.117
0.639
0.000
0.000
0.479
0.016
0.902
0.004
0.378
0.079
0.000
0.006
0.682
0.072
Fe
0.541
0.437
-0.489
-
0.003
0.974
0.003
0.781
0.000
0.345
0.372
0.058
0.096
0.745
0.190
0.580
0.042
0.100
0.670
0.281
0.702
0.079
0.063
Al
0.233
0.175
-0.251
0.822
-
0.470
0.004
0.299
0.003
0.050
0.447
0.267
0.337
0.264
0.738
0.966
0.292
0.308
0.299
0.785
0.463
0.890
0.030
Na
0.786
0.881
-0.846
-0.012
-0.259
-
0.553
0.000
0.831
0.004
0.281
0.011
0.009
0.148
0.062
0.819
0.062
0.984
0.036
0.000
0.000
0.720
0.654
Mg
0.591
0.606
-0.680
0.831
0.821
0.214
-
0.714
0.001
0.603
0.996
0.013
0.019
0.603
0.278
0.448
0.094
0.157
0.855
0.098
0.604
0.250
0.894
Ti
-0.729
-0.828
0.777
0.101
0.365
-0.958
-0.133
-
0.701
0.001
0.270
0.029
0.018
0.351
0.071
0.967
0.126
0.682
0.043
0.001
0.000
0.228
0.005
K
0.452
0.360
-0.431
0.914
0.826
-0.078
0.891
0.139
-
0.243
0.838
0.107
0.176
0.473
0.330
0.378
0.172
0.079
0.921
0.370
0.889
0.051
0.042
P
-0.456
-0.583
0.528
0.335
0.631
-0.819
0.188
0.888
0.407
-
0.655
0.267
0.170
0.283
0.131
0.985
0.402
0.890
0.013
0.051
0.004
0.505
0.052
Mn
-0.176
-0.199
0.170
0.317
0.272
-0.378
0.002
0.386
0.075
0.162
-
0.713
0.866
0.743
0.568
0.685
0.651
0.720
0.986
0.505
0.564
0.000
0.434
LOI
-0.957
-0.973
0.979
-0.616
-0.389
-0.757
-0.748
0.685
-0.540
0.389
0.134
-
0.000
0.654
0.017
0.938
0.001
0.250
0.151
0.000
0.014
0.000
0.009
S
-0.918
-0.973
0.980
-0.554
-0.339
-0.772
-0.721
0.723
-0.465
0.470
0.061
0.981
-
0.744
0.023
0.878
0.003
0.228
0.136
0.000
0.016
0.434
0.997
C
0.223
0.259
-0.254
-0.118
-0.391
0.493
-0.188
-0.331
-0.257
-0.377
-0.119
-0.162
-0.119
-
0.574
0.891
0.558
0.048
0.068
0.434
0.221
0.009
0.745
Cu
-0.805
-0.744
0.730
-0.451
-0.121
-0.609
-0.381
0.592
-0.344
0.511
-0.206
0.728
0.704
-0.203
-
0.545
0.001
0.280
0.061
0.009
0.004
0.009
0.264
Ni
-0.099
0.011
-0.045
0.200
0.015
-0.083
0.272
-0.015
0.313
-0.007
-0.147
-0.028
-0.056
-0.050
0.218
-
0.403
0.269
0.433
0.997
0.969
0.019
0.148
Zn
-0.922
-0.833
0.822
-0.650
-0.370
-0.608
-0.558
0.517
-0.468
0.299
-0.164
0.874
0.833
-0.211
0.865
0.298
-
0.357
0.179
0.004
0.023
0.018
0.603
Pb
-0.381
-0.323
0.313
-0.550
-0.359
0.007
-0.483
0.149
-0.580
0.050
-0.130
0.402
0.419
0.636
0.379
-0.387
0.327
-
0.662
0.382
0.495
0.176
0.017
S
-0.557
-0.599
0.579
-0.155
0.366
-0.664
-0.066
0.646
-0.036
0.745
-0.007
0.490
0.506
-0.598
0.610
-0.280
0.462
0.158
-
0.055
0.005
0.170
0.003
Cl
-0.954
-0.994
0.979
-0.378
-0.099
-0.905
-0.552
0.868
-0.318
0.630
0.239
0.951
0.947
-0.280
0.770
-0.001
0.819
0.311
0.621
-
0.001
0.866
0.008
Ba
-0.829
-0.847
0.799
-0.139
0.263
-0.897
-0.187
0.907
-0.051
0.819
0.208
0.740
0.731
-0.425
0.822
0.014
0.703
0.245
0.804
0.888
-
0.001
0.781
Z
0.945
0.950
0.284
0.651
0.493
0.842
-0.436
0.396
-0.718
-0.325
-0.967
-0.919
-0.924
-0.661
-0.805
-0.744
-0.201
0.257
-0.488
0.627
0.067
-
0.069
Rb
0.939
0.927
0.350
0.777
0.684
0.704
-0.439
0.645
-0.636
-0.207
-0.920
-0.911
-0.873
-0.754
-0.714
-0.732
-0.541
0.099
-0.647
0.848
0.098
-0.411
-0.319

129
b) Ca iglia e al., 2019
Log
(10)
size
Si
Ca
Fe
Al
Na
Mg
Ti
K
P
Mn
S
C
Cu
Ni
Zn
Pb
S
Cl
Log(10)
size
0.00
0.00
0.94
0.89
0.09
0.64
0.00
0.16
0.00
0.03
0.00
0.40
0.50
0.00
0.00
0.00
0.05
0.00
Si
0.91
-
0.00
0.76
0.38
0.28
0.40
0.00
0.57
0.00
0.02
0.00
0.35
0.69
0.00
0.00
0.00
0.04
0.00
Ca
-0.91
-0.96
-
0.66
0.44
0.39
0.75
0.00
0.52
0.00
0.05
0.00
0.44
0.39
0.00
0.02
0.00
0.06
0.00
Fe
0.03
-0.11
-0.16
-
0.84
0.23
0.02
0.95
0.78
0.62
0.21
0.75
0.52
0.43
0.59
0.35
0.89
0.99
0.94
Al
-0.05
0.31
-0.28
-0.07
-
0.11
0.87
0.85
0.14
0.96
0.90
0.37
0.61
0.77
0.52
0.89
0.88
0.65
0.54
Na
0.57
0.38
-0.30
-0.42
-0.54
-
0.10
0.03
0.04
0.06
0.02
0.40
0.29
0.37
0.45
0.04
0.08
0.54
0.21
Mg
-0.17
-0.30
0.12
0.72
-0.06
-0.54
-
0.41
0.96
0.42
0.04
0.76
0.39
0.64
0.86
0.05
0.65
0.24
0.64
Ti
-0.90
-0.83
0.84
-0.02
0.07
-0.69
0.29
-
0.04
0.00
0.01
0.01
0.18
0.26
0.01
0.00
0.00
0.10
0.00
K
-0.48
-0.21
0.23
-0.10
0.51
-0.65
0.02
0.65
-
0.15
0.30
0.78
0.28
0.50
0.72
0.18
0.15
0.55
0.42
P
-0.91
-0.88
0.82
0.18
-0.02
-0.62
0.29
0.87
0.49
-
0.05
0.01
0.59
0.77
0.02
0.00
0.00
0.07
0.00
Mn
-0.67
-0.72
0.62
0.44
-0.05
-0.72
0.66
0.78
0.37
0.63
-
0.05
0.03
0.32
0.07
0.01
0.08
0.26
0.02
S
-0.85
-0.92
0.97
-0.11
-0.32
-0.30
0.11
0.79
0.10
0.75
0.64
-
0.38
0.22
0.00
0.05
0.00
0.17
0.00
C
0.30
0.33
-0.27
-0.23
0.18
0.37
-0.30
-0.46
-0.38
-0.19
-0.68
-0.31
-
0.41
0.45
0.22
0.63
0.55
0.29
Cu
0.24
0.14
-0.31
0.28
-0.10
0.32
0.17
-0.40
-0.24
-0.11
-0.35
-0.43
0.29
-
0.29
0.85
0.44
0.23
0.28
Ni
-0.89
-0.90
0.97
-0.20
-0.23
-0.27
0.06
0.76
0.13
0.72
0.60
0.97
-0.27
-0.37
-
0.06
0.00
0.11
0.00
Zn
-0.81
-0.83
0.72
0.33
-0.05
-0.66
0.63
0.85
0.46
0.86
0.80
0.63
-0.42
0.07
0.62
-
0.01
0.01
0.01
Pb
-0.96
-0.85
0.88
-0.05
0.05
-0.58
0.17
0.88
0.49
0.93
0.58
0.81
-0.17
-0.28
0.84
0.77
-
0.07
0.00
S
-0.63
-0.66
0.61
0.00
-0.16
-0.22
0.41
0.55
0.22
0.60
0.39
0.47
-0.22
0.42
0.53
0.80
0.59
-
0.14
Cl
-0.89
-0.94
0.95
-0.03
-0.22
-0.43
0.17
0.89
0.29
0.85
0.72
0.96
-0.37
-0.38
0.90
0.75
0.83
0.50
-
130
c) Logino a e al., 2019
a)
Log
(10)
size
Si
Ca
Fe
Al
Na
Mg
Ti
Mn
S
C
Cu
Ni
Zn
Pb
Ba
Sb
Log
(10)
size
0.000
0.000
0.001
0.025
0.663
0.778
0.001
0.035
0.000
0.000
0.000
0.000
0.017
0.000
0.074
0.000
Si
0.914
-
0.000
0.000
0.017
0.580
0.214
0.000
0.009
0.000
0.003
0.000
0.000
0.001
0.000
0.008
0.000
Ca
-0.919
-0.954
-
0.004
0.113
0.627
0.356
0.000
0.001
0.000
0.001
0.000
0.000
0.002
0.000
0.018
0.000
Fe
-0.797
-0.817
0.719
-
0.005
0.674
0.385
0.047
0.159
0.010
0.001
0.004
0.000
0.024
0.001
0.179
0.001
Al
-0.595
-0.624
0.442
0.706
-
0.404
0.667
0.164
0.896
0.056
0.058
0.023
0.021
0.080
0.037
0.042
0.032
Na
0.128
-0.162
0.142
0.124
-0.242
-
0.000
0.976
0.255
0.518
0.614
0.733
0.515
0.138
0.722
0.296
0.976
Mg
-0.083
-0.354
0.267
0.252
0.126
0.855
-
0.636
0.294
0.977
0.864
0.228
0.961
0.022
0.262
0.014
0.623
Ti
-0.769
-0.847
0.865
0.539
0.394
0.009
0.139
-
0.005
0.000
0.012
0.002
0.005
0.073
0.003
0.015
0.000
Mn
-0.564
-0.671
0.781
0.398
0.038
0.326
0.302
0.706
-
0.010
0.013
0.010
0.058
0.015
0.004
0.075
0.019
S
-0.956
-0.894
0.935
0.663
0.521
-0.189
-0.008
0.876
0.661
-
0.001
0.000
0.000
0.027
0.000
0.052
0.000
C
-0.823
-0.737
0.803
0.770
0.518
-0.148
-0.050
0.648
0.643
0.805
-
0.001
0.000
0.053
0.000
0.161
0.000
Cu
-0.915
-0.936
0.943
0.711
0.601
0.100
0.344
0.754
0.664
0.891
0.767
-
0.000
0.001
0.000
0.004
0.000
Ni
-0.928
-0.810
0.839
0.810
0.608
-0.190
-0.014
0.706
0.517
0.883
0.916
0.839
-
0.098
0.000
0.121
0.000
Zn
-0.625
-0.788
0.753
0.597
0.484
0.417
0.604
0.493
0.636
0.587
0.527
0.806
0.460
-
0.002
0.003
0.027
Pb
-0.921
-0.919
0.930
0.775
0.560
0.104
0.322
0.726
0.715
0.872
0.827
0.963
0.881
0.743
-
0.021
0.000
Ba
-0.491
-0.672
0.622
0.381
0.549
0.301
0.638
0.633
0.490
0.528
0.396
0.720
0.434
0.723
0.609
-
0.019
Sb
-0.917
-0.924
0.932
0.779
0.573
-0.009
0.144
0.910
0.618
0.934
0.821
0.869
0.897
0.589
0.846
0.618
-
131
d) his wo k: da a om < 2mm g ain size
Log
(10)
size
Si
Ca
Fe
Al
Na
Mg
Ti
K
P
Mn
LOI
Log
(10)
size
0.00
0.01
0.01
0.01
0.16
0.02
0.91
0.00
0.00
0.73
0.00
Si
0.91
-
0.00
0.01
0.00
0.04
0.00
0.75
0.00
0.02
0.82
0.00
Ca
-0.86
-0.99
-
0.01
0.00
0.05
0.00
0.84
0.00
0.04
0.60
0.00
Fe
0.89
0.90
-0.90
-
0.01
0.28
0.00
0.65
0.00
0.01
0.66
0.00
Al
0.86
0.99
-0.98
0.89
-
0.03
0.00
0.87
0.01
0.03
0.70
0.00
Na
0.60
0.79
-0.76
0.48
0.79
-
0.06
0.16
0.21
0.26
0.85
0.05
Mg
0.85
0.98
-1.00
0.91
0.97
0.74
-
0.85
0.00
0.05
0.55
0.00
Ti
-0.05
-0.15
0.09
0.21
-0.08
-0.60
-0.09
-
0.84
0.98
0.29
0.82
K
0.93
0.92
-0.92
0.97
0.89
0.54
0.93
0.10
-
0.02
0.72
0.00
P
0.93
0.84
-0.77
0.87
0.80
0.50
0.76
0.01
0.84
-
0.58
0.01
Mn
-0.16
0.10
-0.24
0.21
0.18
-0.09
0.27
0.47
0.17
-0.26
-
0.87
LOI
-0.92
-1.00
0.98
-0.92
-0.98
-0.76
-0.97
0.11
-0.93
-0.87
-0.08
-
132
APPENDIX II
XRD analysis: phase iden i ica ion and semi-quan i i e es ima ion in XRD pa e n o bulk sample (1)
and colou - based selec ed clas : (2) g ay. (3) g een/ anspa en . (4) me allic pa . (5) whi e. and (6)
ed/da k. The semi-quan i i e con en a e ep esen ed as: xxxx= 70-100 w %. xxx = 40-70 w %.
xx=10-40w %. x=<10 w %. *=unce ain y p esence. Es ima ed e o ±10.
139
APPENDIX VII
S a is ical analysis be ween g ain size and majo and mino elemen s con en ; R2 (lowe iangle) and p alue (uppe iangle) o 5 W E plan s in es iga ed
a) Pa ma W E plan
PARMA
G ain
size
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
As
Ba
Ce
Cl
Co
C
Cu
Ga
H
La
Mo
Nb
Nd
Ni
Pb
Rb
S
Sc
Sn
S
Th
V
Y
Zn
Z
G ain
size
-
9E-08
0.0078
0.528
0.096
0.498
0.050
9E-06
0.002
0.218
0.093
2E-06
0.009
0.002
0.889
2E-05
0.044
0.741
0.006
0.239
0.023
0.464
0.465
0.331
0.217
0.784
0.135
9E-05
7E-06
0.029
0.000
0.052
0.776
0.102
0.024
0.002
1E-04
SiO2
0.988
-
0.0075
0.476
0.095
0.488
0.028
7E-08
0.002
0.200
0.095
7E-09
0.010
0.004
0.655
7E-06
0.055
0.683
0.014
0.306
0.014
0.322
0.423
0.329
0.167
0.980
0.169
5E-05
1E-07
0.022
0.000
0.049
0.804
0.117
0.018
0.005
4E-05
TiO2
-0.780
-0.782
-
0.306
0.901
0.128
0.630
0.005
0.000
0.749
0.000
0.010
0.050
0.000
0.896
0.000
0.011
0.448
0.073
0.709
0.078
0.494
0.243
0.710
0.557
0.972
0.377
0.048
0.007
0.053
0.002
0.022
0.519
0.002
0.526
0.092
0.019
Al2O3
0.227
0.255
0.361
-
0.005
0.404
0.005
0.556
0.528
0.004
0.066
0.399
0.489
0.418
0.204
0.976
0.754
0.217
0.770
0.296
0.440
0.935
0.910
0.003
0.327
0.926
0.458
0.322
0.461
0.808
0.884
0.340
0.065
0.077
0.014
0.543
0.427
Fe2O3
0.555
0.557
0.045
0.809
-
0.360
0.003
0.157
0.850
0.000
0.460
0.101
0.167
0.684
0.542
0.347
0.791
0.728
0.181
0.159
0.147
0.420
0.877
0.063
0.134
0.610
0.131
0.029
0.132
0.564
0.236
0.596
0.095
0.434
0.000
0.135
0.148
MnO
-0.243
-0.249
0.515
0.297
0.325
-
0.924
0.380
0.178
0.853
0.287
0.424
0.221
0.340
0.551
0.252
0.164
0.998
0.797
0.445
0.953
0.982
0.057
0.612
0.954
0.918
0.764
0.566
0.500
0.585
0.559
0.800
0.571
0.301
0.834
0.675
0.360
MgO
0.632
0.689
-0.174
0.805
0.836
-0.035
-
0.031
0.446
0.001
0.772
0.020
0.044
0.568
0.167
0.128
0.671
0.535
0.292
0.298
0.049
0.345
0.583
0.039
0.165
0.463
0.192
0.008
0.025
0.436
0.255
0.691
0.136
0.590
0.000
0.242
0.042
CaO
-0.962
-0.989
0.806
-0.212
-0.483
0.312
-0.679
-
0.001
0.251
0.071
0.000
0.016
0.004
0.567
0.000
0.058
0.569
0.022
0.420
0.022
0.261
0.443
0.356
0.173
0.990
0.273
0.000
0.000
0.012
0.001
0.044
0.998
0.097
0.029
0.010
0.000
Na2O
0.846
0.856
-0.963
-0.227
0.069
-0.463
0.273
-0.886
-
0.918
0.002
0.002
0.084
0.000
0.979
0.000
0.016
0.270
0.048
0.761
0.114
0.371
0.385
0.963
0.332
0.740
0.586
0.023
0.002
0.007
0.002
0.020
0.366
0.002
0.407
0.029
0.002
K2O
0.427
0.443
0.116
0.819
0.907
0.067
0.879
-0.401
-0.038
-
0.320
0.192
0.118
0.940
0.533
0.496
0.607
0.484
0.386
0.245
0.263
0.454
0.936
0.059
0.201
0.400
0.180
0.044
0.251
0.887
0.455
0.870
0.067
0.214
0.000
0.510
0.257
P2O5
-0.559
-0.557
0.909
0.601
0.265
0.374
0.105
0.593
-0.841
0.351
-
0.133
0.198
0.001
0.994
0.019
0.063
0.315
0.113
0.626
0.167
0.361
0.445
0.345
0.757
0.964
0.463
0.205
0.084
0.094
0.024
0.007
0.325
0.004
0.969
0.238
0.208
LOI
-0.975
-0.994
0.763
-0.300
-0.548
0.286
-0.716
0.989
-0.849
-0.450
0.509
-
0.013
0.008
0.619
0.000
0.047
0.722
0.024
0.376
0.021
0.369
0.400
0.257
0.161
0.918
0.232
0.000
0.000
0.024
0.002
0.091
0.832
0.129
0.018
0.007
0.000
As
-0.768
-0.765
0.633
-0.249
-0.473
0.425
-0.646
0.731
-0.572
-0.527
0.445
0.747
-
0.064
0.578
0.020
0.086
0.328
0.149
0.090
0.004
0.474
0.041
0.552
0.338
0.447
0.006
0.007
0.008
0.580
0.023
0.214
0.110
0.614
0.020
0.302
0.069
Ba
-0.842
-0.820
0.931
0.289
-0.147
0.338
-0.206
0.822
-0.932
-0.028
0.869
0.780
0.604
-
0.728
0.000
0.076
0.245
0.007
0.421
0.104
0.324
0.611
0.930
0.299
0.912
0.296
0.016
0.007
0.026
0.000
0.002
0.497
0.003
0.332
0.024
0.014
Ce
0.051
0.162
0.047
0.440
0.220
0.215
0.474
-0.206
0.009
0.224
-0.003
-0.180
-0.201
0.126
-
0.885
0.943
0.531
0.866
0.320
0.143
0.132
0.604
0.299
0.288
0.293
0.576
0.665
0.463
0.949
0.671
0.960
0.414
0.322
0.307
0.869
0.864
Cl
-0.954
-0.964
0.909
-0.011
-0.333
0.400
-0.514
0.974
-0.956
-0.244
0.721
0.955
0.717
0.914
-0.053
-
0.030
0.459
0.018
0.511
0.038
0.347
0.392
0.622
0.254
0.917
0.300
0.001
0.000
0.011
0.000
0.023
0.779
0.022
0.100
0.012
0.000
Co
-0.645
-0.621
0.756
0.114
0.096
0.477
-0.154
0.615
-0.734
0.186
0.606
0.638
0.569
0.584
-0.026
0.683
-
0.547
0.292
0.568
0.142
0.544
0.088
0.810
0.869
0.251
0.390
0.238
0.032
0.298
0.100
0.604
0.949
0.069
0.729
0.129
0.067
C
0.120
0.148
-0.271
-0.429
-0.126
0.001
-0.224
-0.205
0.386
-0.251
-0.354
-0.129
0.346
-0.405
-0.226
-0.265
0.217
-
0.608
0.194
0.444
0.143
0.247
0.403
0.345
0.987
0.114
0.785
0.853
0.028
0.466
0.073
0.003
0.094
0.547
0.480
0.473
Cu
-0.796
-0.743
0.589
-0.106
-0.460
-0.094
-0.370
0.710
-0.637
-0.309
0.532
0.700
0.492
0.786
0.062
0.724
0.371
-0.186
-
0.059
0.132
0.702
0.501
0.236
0.406
0.526
0.141
0.012
0.024
0.124
0.002
0.048
0.983
0.148
0.081
0.001
0.037
Ga
-0.410
-0.361
0.135
-0.368
-0.482
-0.273
-0.366
0.288
-0.110
-0.405
0.176
0.315
0.564
0.287
-0.351
0.236
0.206
0.448
0.614
-
0.066
0.730
0.861
0.141
0.383
0.965
0.004
0.215
0.287
0.752
0.270
0.508
0.075
0.647
0.080
0.283
0.670
H
0.704
0.741
-0.581
0.276
0.494
0.021
0.635
-0.707
0.531
0.392
-0.473
-0.711
-0.821
-0.544
0.498
-0.658
-0.499
-0.274
-0.510
-0.601
-
0.315
0.183
0.586
0.376
0.259
0.004
0.022
0.006
0.544
0.043
0.159
0.112
0.614
0.023
0.183
0.124
La
0.262
0.350
-0.246
0.030
0.288
-0.008
0.334
-0.393
0.318
0.268
-0.324
-0.319
-0.257
-0.348
0.510
-0.333
0.218
0.498
-0.139
-0.125
0.354
-
0.733
0.858
0.012
0.064
0.801
0.245
0.359
0.181
0.448
0.032
0.742
0.869
0.350
0.894
0.478
Mo
-0.262
-0.286
0.407
0.041
0.056
0.617
-0.198
0.274
-0.309
-0.029
0.273
0.300
0.651
0.184
-0.187
0.305
0.566
0.404
-0.242
0.064
-0.459
-0.124
-
0.528
0.719
0.439
0.289
0.604
0.345
0.881
0.634
0.917
0.271
0.829
0.764
0.626
0.596
Nb
0.344
0.345
0.135
0.826
0.607
0.183
0.658
-0.328
0.017
0.614
0.335
-0.396
-0.214
0.032
0.365
-0.178
-0.088
-0.298
-0.413
-0.500
0.197
-0.065
0.227
-
0.272
0.413
0.630
0.285
0.322
0.899
0.782
0.496
0.406
0.445
0.038
0.214
0.215
Nd
0.428
0.474
-0.212
0.346
0.508
-0.021
0.476
-0.468
0.343
0.442
-0.113
-0.479
-0.339
-0.366
0.374
-0.398
0.060
0.334
-0.296
-0.310
0.315
0.755
-0.131
0.385
-
0.396
0.701
0.199
0.229
0.299
0.299
0.220
0.987
0.828
0.117
0.426
0.155
Ni
-0.100
-0.009
0.013
0.034
0.184
0.037
0.263
-0.005
-0.121
0.300
-0.016
0.038
-0.272
0.040
0.370
0.038
0.401
-0.006
0.228
-0.016
0.395
0.604
-0.277
-0.292
0.302
-
0.360
0.787
0.985
0.521
0.975
0.483
0.329
0.491
0.438
0.221
0.627
Pb
-0.507
-0.471
0.314
-0.266
-0.512
-0.109
-0.450
0.385
-0.197
-0.461
0.263
0.415
0.795
0.368
-0.202
0.365
0.306
0.532
0.500
0.811
-0.820
-0.092
0.373
-0.174
-0.139
-0.325
-
0.106
0.147
0.662
0.112
0.376
0.008
0.850
0.046
0.405
0.577
Rb
0.932
0.939
-0.636
0.350
0.684
-0.207
0.777
-0.927
0.704
0.645
-0.439
-0.920
-0.790
-0.732
0.157
-0.873
-0.411
0.099
-0.754
-0.430
0.707
0.406
-0.188
0.376
0.444
0.098
-0.541
-
0.000
0.045
0.002
0.043
0.565
0.368
0.003
0.020
0.002
S
-0.964
-0.988
0.789
-0.264
-0.511
0.242
-0.698
0.984
-0.851
-0.401
0.572
0.986
0.776
0.784
-0.263
0.951
0.677
-0.067
0.702
0.374
-0.798
-0.325
0.334
-0.350
-0.419
-0.007
0.493
-0.911
-
0.034
0.002
0.075
0.720
0.137
0.021
0.009
0.000
Sc
-0.685
-0.709
0.625
0.088
-0.208
0.197
-0.279
0.753
-0.784
-0.052
0.558
0.702
0.200
0.696
-0.023
0.756
0.366
-0.687
0.519
-0.115
-0.218
-0.460
-0.055
-0.046
-0.366
0.231
-0.159
-0.642
0.669
-
0.049
0.024
0.120
0.049
0.534
0.026
0.010
Sn
-0.929
-0.896
0.843
0.053
-0.413
0.211
-0.398
0.863
-0.850
-0.267
0.702
0.855
0.703
0.946
0.154
0.919
0.549
-0.261
0.847
0.386
-0.647
-0.271
0.172
-0.101
-0.365
0.011
0.533
-0.847
0.851
0.633
-
0.008
0.992
0.027
0.097
0.006
0.005
S
-0.628
-0.634
0.707
0.338
-0.192
0.092
-0.144
0.645
-0.715
-0.060
0.790
0.562
0.431
0.847
-0.018
0.703
0.188
-0.590
0.637
0.238
-0.481
-0.675
0.038
0.244
-0.426
-0.252
0.315
-0.647
0.586
0.700
0.781
-
0.470
0.067
0.436
0.137
0.153
Th
-0.104
-0.090
-0.232
-0.604
-0.556
-0.204
-0.506
-0.001
0.321
-0.599
-0.348
0.077
0.536
-0.244
-0.291
-0.102
0.023
0.829
-0.008
0.586
-0.534
0.120
0.386
-0.296
0.006
-0.345
0.776
-0.208
0.130
-0.524
-0.004
-0.259
-
0.068
0.089
0.813
0.784
V
-0.546
-0.527
0.856
0.583
0.279
0.364
0.195
0.554
-0.849
0.431
0.813
0.513
0.182
0.824
0.349
0.707
0.595
-0.558
0.492
-0.166
-0.183
-0.060
0.079
0.273
-0.079
0.247
-0.069
-0.319
0.504
0.635
0.690
0.600
-0.599
-
0.725
0.098
0.085
Y
0.700
0.724
-0.228
0.743
0.900
0.076
0.941
-0.683
0.295
0.897
0.014
-0.724
-0.714
-0.343
0.360
-0.549
-0.126
-0.217
-0.577
-0.579
0.705
0.331
-0.109
0.660
0.527
0.278
-0.640
0.828
-0.711
-0.224
-0.554
-0.279
-0.564
0.128
-
0.130
0.050
Zn
-0.845
-0.805
0.561
-0.219
-0.507
-0.152
-0.408
0.762
-0.684
-0.237
0.411
0.789
0.364
0.702
0.060
0.753
0.514
-0.254
0.860
0.377
-0.458
-0.049
-0.177
-0.430
-0.284
0.425
0.297
-0.714
0.772
0.694
0.796
0.504
-0.086
0.552
-0.512
-
0.005
Z
0.930
0.945
-0.718
0.284
0.493
-0.325
0.651
-0.950
0.842
0.396
-0.436
-0.967
-0.596
-0.744
0.062
-0.924
-0.600
0.257
-0.661
-0.154
0.520
0.254
-0.191
0.430
0.486
-0.176
-0.201
0.848
-0.919
-0.764
-0.801
-0.488
0.100
-0.570
0.633
-0.805
-

140
b) Piacenza W E plan
PIACENZA
G ain size
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
As
Ba
Ce
Cl
Co
C
Cu
Ga
La
Mo
Nb
Nd
Ni
Pb
Rb
S
Sc
Sn
S
Th
V
Y
Zn
Z
G ain size
-
0.003
0.050
0.001
0.091
0.269
0.796
0.014
0.014
0.657
0.113
0.161
0.318
0.656
0.289
0.008
0.973
0.159
0.002
0.065
0.844
0.107
0.871
0.620
0.849
0.289
0.766
0.133
0.116
0.073
0.073
0.128
0.236
0.952
0.098
0.235
SiO2
0.919
-
0.049
0.000
0.009
0.744
0.675
0.000
0.012
0.657
0.066
0.105
0.295
0.447
0.154
0.001
0.910
0.212
0.004
0.014
0.373
0.036
0.974
0.824
0.572
0.183
0.690
0.028
0.107
0.168
0.045
0.078
0.248
0.486
0.141
0.169
TiO2
-0.755
-0.756
-
0.027
0.116
0.536
0.304
0.026
0.001
0.055
0.005
0.410
0.009
0.067
0.016
0.004
0.548
0.999
0.026
0.031
0.723
0.011
0.149
0.817
0.722
0.009
0.072
0.012
0.007
0.012
0.000
0.001
0.008
0.456
0.002
0.999
Al2O3
-0.944
-0.972
0.812
-
0.016
0.671
0.783
0.000
0.010
0.529
0.048
0.249
0.231
0.389
0.105
0.001
0.846
0.255
0.004
0.007
0.671
0.040
0.900
0.609
0.574
0.168
0.599
0.030
0.078
0.137
0.043
0.062
0.240
0.499
0.114
0.272
Fe2O3
0.682
0.880
-0.647
-0.848
-
0.620
0.657
0.002
0.080
0.703
0.128
0.292
0.261
0.193
0.078
0.015
0.522
0.507
0.084
0.001
0.242
0.018
0.955
0.645
0.256
0.117
0.642
0.014
0.313
0.359
0.082
0.094
0.417
0.084
0.348
0.420
MnO
-0.486
-0.152
0.285
0.198
0.230
-
0.685
0.988
0.504
0.907
0.957
0.587
0.798
0.585
0.631
0.740
0.336
0.682
0.424
0.770
0.495
0.930
0.536
0.918
0.297
0.991
0.931
0.700
0.507
0.135
0.633
0.859
0.448
0.061
0.315
0.828
MgO
0.121
0.195
0.456
-0.129
0.207
0.189
-
0.823
0.492
0.011
0.328
0.845
0.058
0.119
0.295
0.828
0.301
0.122
0.897
0.981
0.770
0.471
0.002
0.347
0.044
0.144
0.009
0.586
0.414
0.213
0.298
0.218
0.063
0.797
0.134
0.041
CaO
-0.855
-0.972
0.812
0.972
-0.930
0.007
-0.105
-
0.012
0.472
0.033
0.236
0.185
0.244
0.054
0.000
0.839
0.377
0.012
0.001
0.421
0.015
0.849
0.760
0.493
0.100
0.492
0.006
0.083
0.186
0.028
0.038
0.220
0.266
0.129
0.319
Na2O
0.855
0.863
-0.948
-0.875
0.699
-0.306
-0.315
-0.865
-
0.125
0.003
0.139
0.032
0.151
0.038
0.001
0.717
0.561
0.001
0.033
0.587
0.006
0.289
0.857
0.677
0.025
0.149
0.011
0.026
0.017
0.001
0.003
0.015
0.520
0.003
0.676
K2O
-0.206
-0.207
0.745
0.289
-0.177
0.055
0.872
0.328
-0.636
-
0.031
0.911
0.007
0.029
0.031
0.259
0.460
0.393
0.367
0.360
0.901
0.127
0.023
0.520
0.186
0.027
0.000
0.126
0.107
0.136
0.070
0.025
0.015
0.426
0.028
0.233
P2O5
-0.651
-0.724
0.903
0.758
-0.632
0.025
0.436
0.793
-0.921
0.800
-
0.320
0.020
0.069
0.005
0.008
0.778
0.771
0.024
0.043
0.687
0.010
0.274
0.788
0.617
0.018
0.040
0.004
0.029
0.102
0.008
0.001
0.021
0.291
0.012
0.935
LOI
-0.592
-0.662
0.373
0.504
-0.466
0.251
-0.091
0.516
-0.618
0.052
0.442
-
0.609
0.885
0.707
0.178
0.818
0.189
0.066
0.486
0.136
0.220
0.897
0.502
0.635
0.457
0.864
0.306
0.531
0.301
0.236
0.346
0.292
0.967
0.294
0.209
As
-0.444
-0.463
0.882
0.520
-0.493
0.120
0.738
0.566
-0.798
0.894
0.832
0.237
-
0.003
0.008
0.076
0.693
0.525
0.164
0.098
0.785
0.012
0.016
0.758
0.431
0.000
0.005
0.034
0.108
0.024
0.006
0.001
0.005
0.243
0.009
0.350
Ba
-0.207
-0.346
0.722
0.388
-0.558
-0.252
0.643
0.508
-0.604
0.804
0.719
0.068
0.918
-
0.005
0.172
0.982
0.321
0.423
0.084
0.600
0.021
0.056
0.837
0.797
0.002
0.013
0.033
0.279
0.186
0.045
0.015
0.069
0.038
0.119
0.248
Ce
-0.469
-0.600
0.846
0.663
-0.703
-0.223
0.464
0.747
-0.780
0.800
0.908
0.175
0.884
0.908
-
0.032
0.921
0.799
0.144
0.015
0.709
0.006
0.216
0.963
0.960
0.005
0.026
0.002
0.104
0.184
0.019
0.002
0.068
0.057
0.066
0.660
Cl
-0.887
-0.950
0.910
0.960
-0.851
0.155
0.102
0.969
-0.962
0.495
0.884
0.574
0.707
0.580
0.795
-
0.971
0.448
0.002
0.005
0.502
0.005
0.538
0.908
0.868
0.043
0.284
0.004
0.042
0.064
0.005
0.008
0.076
0.352
0.033
0.478
Co
0.016
0.053
0.276
-0.091
0.294
0.430
0.458
-0.095
-0.169
0.337
0.132
0.108
0.184
0.011
-0.046
0.017
-
0.356
0.977
0.587
0.625
0.913
0.315
0.017
0.257
0.745
0.498
0.966
0.180
0.463
0.542
0.710
0.266
0.339
0.321
0.950
C
-0.595
-0.539
0.001
0.499
-0.304
0.191
-0.639
0.398
-0.268
-0.386
0.136
0.562
-0.292
-0.442
-0.119
0.345
-0.414
-
0.192
0.664
0.968
0.869
0.144
0.368
0.664
0.586
0.315
0.869
0.964
0.960
0.964
0.910
0.697
0.656
0.944
0.033
Cu
-0.941
-0.917
0.814
0.914
-0.694
0.363
0.061
0.866
-0.947
0.405
0.818
0.724
0.589
0.364
0.612
0.936
0.013
0.559
-
0.057
0.659
0.034
0.647
0.887
0.819
0.140
0.428
0.049
0.091
0.057
0.027
0.041
0.096
0.727
0.038
0.344
Ga
-0.725
-0.854
0.799
0.890
-0.947
-0.137
0.011
0.944
-0.794
0.411
0.769
0.319
0.673
0.694
0.853
0.909
-0.251
0.202
0.740
-
0.545
0.006
0.655
0.544
0.421
0.046
0.349
0.004
0.168
0.205
0.034
0.027
0.245
0.087
0.172
0.704
La
-0.092
-0.401
0.165
0.197
-0.510
-0.312
-0.137
0.365
-0.251
-0.058
0.187
0.622
0.128
0.243
0.174
0.307
0.227
-0.019
0.205
0.278
-
0.353
0.934
0.182
0.697
0.460
0.905
0.314
0.708
0.848
0.420
0.555
0.594
0.378
0.770
0.439
Mo
-0.660
-0.786
0.871
0.777
-0.839
-0.041
0.329
0.851
-0.897
0.633
0.876
0.531
0.864
0.829
0.898
0.906
-0.051
0.077
0.791
0.895
0.416
-
0.238
0.957
0.956
0.002
0.101
0.001
0.136
0.064
0.002
0.001
0.039
0.105
0.038
0.997
Nb
-0.076
-0.016
0.606
0.059
-0.027
0.285
0.936
0.089
-0.468
0.824
0.481
0.061
0.846
0.742
0.535
0.284
0.447
-0.613
0.213
0.207
0.039
0.514
-
0.389
0.123
0.046
0.016
0.387
0.317
0.059
0.118
0.106
0.022
0.668
0.061
0.085
Nd
-0.230
-0.104
-0.108
0.237
-0.214
-0.048
-0.421
0.143
0.084
-0.295
-0.126
-0.308
-0.144
-0.097
0.022
0.054
-0.845
0.404
0.067
0.279
-0.569
-0.025
-0.388
-
0.252
0.687
0.454
0.842
0.445
0.782
0.632
0.742
0.332
0.755
0.521
0.945
Ni
0.089
0.261
0.166
-0.260
0.498
0.462
0.767
-0.314
-0.194
0.565
0.232
0.220
0.358
0.120
0.024
-0.078
0.497
-0.202
0.107
-0.365
-0.181
0.026
0.638
-0.501
-
0.652
0.211
0.864
0.711
0.371
0.682
0.637
0.197
0.419
0.280
0.336
Pb
-0.468
-0.568
0.881
0.584
-0.645
-0.006
0.612
0.669
-0.818
0.810
0.840
0.339
0.971
0.941
0.909
0.770
0.152
-0.252
0.617
0.763
0.337
0.935
0.763
-0.188
0.209
-
0.016
0.008
0.109
0.041
0.002
0.000
0.009
0.130
0.018
0.525
Rb
-0.139
-0.186
0.713
0.244
-0.216
-0.041
0.879
0.315
-0.607
0.987
0.777
0.080
0.907
0.862
0.813
0.472
0.311
-0.447
0.360
0.419
0.056
0.667
0.849
-0.341
0.540
0.849
-
0.108
0.155
0.160
0.068
0.024
0.016
0.301
0.042
0.193
S
-0.625
-0.808
0.866
0.802
-0.857
-0.179
0.252
0.897
-0.870
0.634
0.916
0.455
0.792
0.794
0.930
0.915
0.020
0.077
0.757
0.911
0.448
0.954
0.390
-0.093
-0.080
0.883
0.658
-
0.065
0.163
0.006
0.002
0.066
0.084
0.059
0.813
Sc
-0.647
-0.659
0.889
0.703
-0.449
0.304
0.370
0.696
-0.813
0.659
0.805
0.288
0.658
0.477
0.664
0.772
0.572
-0.021
0.682
0.585
0.175
0.621
0.445
-0.347
0.173
0.657
0.599
0.725
-
0.090
0.023
0.037
0.036
0.836
0.014
0.709
Sn
-0.712
-0.585
0.867
0.620
-0.411
0.623
0.538
0.565
-0.845
0.621
0.667
0.459
0.820
0.565
0.567
0.727
0.335
-0.024
0.741
0.546
0.090
0.726
0.736
-0.130
0.402
0.774
0.594
0.590
0.684
-
0.010
0.030
0.008
0.918
0.003
0.801
S
-0.711
-0.766
0.970
0.770
-0.696
0.222
0.461
0.807
-0.950
0.716
0.887
0.515
0.898
0.766
0.835
0.905
0.281
-0.021
0.810
0.792
0.366
0.931
0.644
-0.222
0.191
0.933
0.720
0.899
0.824
0.873
-
0.000
0.004
0.354
0.002
0.994
Th
-0.632
-0.703
0.956
0.731
-0.678
0.083
0.533
0.781
-0.928
0.817
0.947
0.422
0.945
0.850
0.929
0.883
0.173
-0.053
0.773
0.810
0.272
0.949
0.661
-0.154
0.219
0.963
0.821
0.931
0.785
0.803
0.972
-
0.005
0.221
0.004
0.812
V
-0.516
-0.505
0.885
0.512
-0.368
0.346
0.729
0.531
-0.852
0.853
0.829
0.466
0.909
0.718
0.721
0.706
0.489
-0.181
0.676
0.508
0.247
0.779
0.827
-0.433
0.554
0.880
0.848
0.723
0.785
0.883
0.918
0.905
-
0.642
0.000
0.653
Y
0.028
0.319
-0.340
-0.310
0.693
0.733
-0.120
-0.489
0.296
-0.361
-0.467
-0.019
-0.509
-0.780
-0.740
-0.417
0.427
0.207
-0.163
-0.689
-0.397
-0.663
-0.199
-0.146
0.367
-0.629
-0.458
-0.693
-0.097
-0.048
-0.415
-0.530
-0.216
-
0.762
0.619
Zn
0.672
0.616
-0.942
-0.650
0.420
-0.447
-0.624
-0.630
0.919
-0.808
-0.864
-0.464
-0.879
-0.644
-0.723
-0.794
-0.442
0.033
-0.782
-0.580
-0.137
-0.780
-0.732
0.295
-0.476
-0.838
-0.773
-0.736
-0.854
-0.921
-0.933
-0.911
-0.973
0.141
-
0.857
Z
0.516
0.584
0.000
-0.483
0.366
-0.102
0.775
-0.443
0.194
0.519
-0.038
-0.542
0.418
0.505
0.205
-0.324
0.029
-0.793
-0.424
-0.177
-0.352
-0.001
0.692
-0.032
0.430
0.292
0.558
-0.111
-0.174
0.118
-0.004
0.111
0.209
-0.231
-0.085
-
141
c) To ino W E plan
TORINO
G ain size
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
As
Ba
Ce
Cl
Co
C
Cu
Ga
La
Mo
Nb
Nd
Ni
Pb
Rb
S
Sc
Sn
S
Th
V
Y
Zn
Z
G ain size
-
0.023
0.008
0.002
0.025
0.469
0.415
0.003
0.048
0.128
0.611
3E-07
0.235
0.006
0.036
0.009
0.612
0.000
0.000
0.014
0.068
0.771
0.563
0.928
0.727
0.143
0.899
0.019
0.261
0.001
0.000
0.263
0.098
0.165
3E-05
0.232
SiO2
0.704
-
0.680
0.261
0.999
0.005
0.326
0.551
0.016
0.829
0.371
0.053
0.756
0.542
0.703
0.000
0.338
0.011
0.154
0.518
0.298
0.250
0.512
0.262
0.075
0.824
0.075
0.681
0.908
0.293
0.110
0.977
0.040
0.244
0.0781
0.403
TiO2
-0.775
-0.149
-
0.001
0.000
0.545
0.043
0.000
0.403
0.027
0.350
0.002
0.049
0.001
0.027
0.377
0.192
0.069
0.002
0.000
0.123
0.978
0.632
0.291
0.547
0.008
0.370
0.000
0.053
0.000
0.003
0.028
0.256
0.433
0.0126
0.270
Al2O3
-0.849
-0.393
0.866
-
0.016
0.742
0.365
0.002
0.277
0.054
0.289
0.002
0.182
0.017
0.018
0.106
0.493
0.052
0.001
0.007
0.029
0.948
0.663
0.955
0.698
0.101
0.607
0.013
0.023
0.003
0.009
0.068
0.161
0.327
0.0030
0.083
Fe2O3
0.697
0.000
-0.910
-0.735
-
0.163
0.004
7E-06
0.495
0.002
0.068
0.010
0.268
0.000
0.009
0.583
0.052
0.096
0.003
0.009
0.178
0.338
0.745
0.202
0.324
0.090
0.081
0.004
0.133
0.003
0.003
0.145
0.738
0.498
0.0090
0.573
MnO
-0.260
-0.800
-0.218
0.120
0.478
-
0.017
0.468
0.137
0.219
0.088
0.681
0.866
0.409
0.510
0.026
0.013
0.450
0.900
0.808
0.825
0.113
0.521
0.032
0.037
0.662
0.018
0.543
0.696
0.840
0.979
0.639
0.073
0.750
0.8009
0.426
MgO
-0.291
0.347
0.647
0.321
-0.813
-0.726
-
0.043
0.718
0.011
0.222
0.245
0.539
0.005
0.192
0.795
0.027
0.642
0.135
0.115
0.733
0.372
0.350
0.034
0.541
0.269
0.029
0.108
0.263
0.187
0.106
0.289
0.980
0.888
0.1929
0.328
CaO
-0.835
-0.215
0.937
0.845
-0.965
-0.260
0.648
-
0.327
0.006
0.102
0.001
0.207
0.000
0.003
0.286
0.124
0.022
0.000
0.004
0.107
0.484
0.819
0.390
0.429
0.069
0.223
0.002
0.162
0.000
0.000
0.135
0.503
0.283
0.0015
0.258
Na2O
0.635
0.733
-0.298
-0.382
0.245
-0.504
-0.131
-0.346
-
0.277
0.629
0.052
0.767
0.134
0.770
0.000
0.567
0.075
0.035
0.394
0.465
0.813
0.011
0.347
0.011
0.999
0.833
0.724
0.895
0.459
0.042
0.935
0.009
0.974
0.0497
0.879
K2O
-0.515
0.079
0.690
0.624
-0.856
-0.426
0.761
0.798
-0.381
-
0.016
0.090
0.845
0.003
0.032
0.489
0.146
0.379
0.010
0.176
0.325
0.058
0.290
0.763
0.596
0.698
0.004
0.191
0.205
0.147
0.035
0.554
0.795
0.915
0.0300
0.874
P2O5
-0.184
0.318
0.331
0.373
-0.598
-0.566
0.424
0.547
0.175
0.730
-
0.615
0.498
0.228
0.020
0.658
0.086
0.805
0.302
0.884
0.491
0.002
0.456
0.897
0.032
0.749
0.004
0.609
0.567
0.446
0.449
0.978
0.147
0.748
0.3019
0.453
LOI
-0.984
-0.625
0.839
0.846
-0.766
0.149
0.405
0.875
-0.627
0.563
0.182
-
0.152
0.001
0.047
0.019
0.439
0.000
3E-05
0.004
0.046
0.772
0.493
0.712
0.770
0.072
0.971
0.007
0.193
0.000
0.000
0.148
0.078
0.189
4E-05
0.298
As
-0.413
-0.113
0.635
0.459
-0.388
-0.062
0.221
0.437
0.108
-0.071
-0.243
0.489
-
0.314
0.515
0.986
0.428
0.210
0.359
0.005
0.233
0.070
0.560
0.082
0.523
0.000
0.363
0.004
0.227
0.023
0.252
0.002
0.295
0.133
0.452
0.310
Ba
-0.794
-0.219
0.876
0.726
-0.941
-0.294
0.801
0.929
-0.508
0.830
0.419
0.859
0.355
-
0.022
0.207
0.086
0.032
0.000
0.009
0.186
0.600
0.316
0.250
0.888
0.121
0.200
0.011
0.184
0.005
0.000
0.180
0.309
0.455
0.001
0.848
Ce
0.664
0.138
-0.690
-0.723
0.771
0.237
-0.450
-0.832
0.107
-0.675
-0.714
-0.638
-0.234
-0.709
-
0.516
0.114
0.074
0.030
0.127
0.368
0.305
0.613
0.456
0.157
0.348
0.215
0.060
0.494
0.011
0.031
0.419
0.844
0.099
0.019
0.188
Cl
-0.774
-0.919
0.314
0.542
-0.198
0.695
-0.095
0.375
-0.912
0.248
-0.160
0.718
0.006
0.437
-0.233
-
0.467
0.018
0.028
0.354
0.237
0.532
0.115
0.219
0.042
0.891
0.424
0.597
0.720
0.257
0.035
0.931
0.010
0.518
0.019
0.571
Co
0.184
-0.339
-0.450
-0.246
0.629
0.745
-0.691
-0.520
-0.207
-0.495
-0.570
-0.277
-0.283
-0.569
0.531
0.261
-
0.591
0.352
0.338
0.531
0.371
0.645
0.036
0.131
0.310
0.115
0.211
0.392
0.247
0.289
0.291
0.525
0.497
0.374
0.966
C
-0.912
-0.759
0.596
0.628
-0.554
0.270
0.168
0.708
-0.586
0.313
0.090
0.900
0.434
0.675
-0.588
0.722
-0.194
-
0.007
0.057
0.091
0.679
0.953
0.746
0.747
0.156
0.545
0.054
0.798
0.004
0.001
0.335
0.170
0.023
0.002
0.270
Cu
-0.917
-0.486
0.855
0.877
-0.828
0.046
0.507
0.909
-0.666
0.767
0.363
0.946
0.325
0.907
-0.683
0.686
-0.330
0.783
-
0.009
0.043
0.750
0.293
0.909
0.837
0.162
0.440
0.022
0.140
0.004
0.000
0.172
0.093
0.359
0.000
0.330
Ga
-0.743
-0.233
0.952
0.786
-0.773
-0.088
0.530
0.821
-0.303
0.465
0.053
0.818
0.805
0.774
-0.516
0.328
-0.339
0.618
0.769
-
0.134
0.476
0.642
0.231
0.794
0.000
0.862
0.000
0.082
0.000
0.008
0.008
0.111
0.345
0.040
0.279
La
0.598
0.366
-0.520
-0.683
0.463
-0.081
-0.124
-0.541
0.262
-0.347
-0.247
-0.640
-0.415
-0.455
0.319
-0.411
0.225
-0.562
-0.648
-0.508
-
0.801
0.947
0.816
0.677
0.204
0.982
0.168
0.042
0.083
0.096
0.033
0.225
0.193
0.040
0.246
Mo
-0.106
-0.402
-0.010
0.024
0.339
0.532
-0.317
-0.251
-0.086
-0.617
-0.844
0.105
0.595
-0.189
0.361
0.225
0.318
0.150
-0.116
0.256
-0.092
-
0.774
0.700
0.231
0.208
0.003
0.678
0.668
0.768
0.915
0.243
0.082
0.522
0.856
0.931
Nb
-0.209
-0.236
0.174
0.158
-0.118
0.231
0.331
0.083
-0.761
0.372
-0.267
0.246
-0.210
0.354
0.183
0.530
0.167
0.022
0.370
0.168
0.024
0.104
-
0.592
0.010
0.777
0.666
0.876
0.506
0.830
0.419
0.947
0.031
0.167
0.448
0.194
Nd
0.033
-0.392
-0.371
0.020
0.441
0.675
-0.670
-0.306
-0.333
-0.110
-0.047
-0.134
-0.575
-0.401
0.267
0.426
0.666
-0.118
-0.042
-0.417
-0.085
-0.140
0.194
-
0.253
0.075
0.681
0.132
0.808
0.264
0.541
0.187
0.582
0.388
0.839
0.396
Ni
-0.127
-0.586
-0.217
-0.141
0.348
0.662
-0.220
-0.283
-0.759
-0.192
-0.674
0.106
-0.230
-0.051
0.483
0.649
0.512
0.117
0.075
-0.095
0.151
0.417
0.766
0.399
-
0.514
0.215
0.399
0.644
0.472
0.807
0.435
0.025
0.385
0.872
0.320
Pb
-0.498
-0.081
0.775
0.549
-0.563
-0.159
0.387
0.596
0.000
0.141
-0.116
0.591
0.969
0.523
-0.332
0.050
-0.358
0.485
0.478
0.906
-0.440
0.436
-0.103
-0.586
-0.235
-
0.709
0.000
0.187
0.007
0.111
0.001
0.257
0.195
0.286
0.298
Rb
0.046
0.586
0.318
0.186
-0.576
-0.725
0.685
0.423
0.077
0.818
0.810
0.013
-0.323
0.443
-0.430
-0.285
-0.531
-0.218
0.276
0.063
0.008
-0.837
0.156
-0.149
-0.430
-0.135
-
0.774
0.509
0.887
0.663
0.941
0.301
0.374
0.650
0.758
S
-0.720
-0.149
0.942
0.750
-0.819
-0.219
0.539
0.856
-0.128
0.451
0.185
0.786
0.812
0.756
-0.611
0.191
-0.434
0.624
0.709
0.964
-0.473
0.151
-0.057
-0.510
-0.300
0.905
0.104
-
0.130
0.000
0.011
0.017
0.380
0.241
0.051
0.209
Sc
0.393
-0.042
-0.625
-0.705
0.509
0.142
-0.392
-0.478
0.048
-0.439
-0.207
-0.449
-0.420
-0.457
0.245
-0.130
0.305
-0.093
-0.501
-0.575
0.650
-0.155
-0.239
0.088
0.167
-0.455
-0.237
-0.512
-
0.191
0.320
0.031
0.302
0.819
0.195
0.649
Sn
-0.875
-0.369
0.911
0.833
-0.826
-0.074
0.454
0.912
-0.265
0.494
0.273
0.902
0.705
0.806
-0.756
0.396
-0.404
0.812
0.817
0.900
-0.573
0.107
-0.078
-0.391
-0.258
0.786
0.052
0.943
-0.450
-
0.001
0.044
0.346
0.073
0.004
0.154
S
-0.944
-0.536
0.831
0.771
-0.831
0.009
0.542
0.906
-0.649
0.668
0.271
0.974
0.400
0.930
-0.679
0.667
-0.373
0.885
0.954
0.780
-0.554
-0.039
0.288
-0.220
0.089
0.536
0.158
0.757
-0.351
0.871
-
0.224
0.141
0.215
0.000
0.486
Th
-0.392
0.011
0.688
0.597
-0.496
-0.170
0.373
0.506
0.030
0.213
-0.010
0.493
0.856
0.461
-0.288
0.031
-0.371
0.341
0.468
0.779
-0.673
0.407
-0.024
-0.455
-0.279
0.866
-0.027
0.729
-0.679
0.645
0.423
-
0.206
0.197
0.274
0.428
V
-0.552
-0.654
0.397
0.479
-0.122
0.590
0.009
0.241
-0.772
0.094
-0.494
0.581
0.368
0.358
0.072
0.764
0.229
0.470
0.559
0.535
-0.422
0.574
0.677
0.199
0.698
0.396
-0.364
0.312
-0.363
0.334
0.500
0.437
-
0.820
0.177
0.779
Y
0.475
0.406
-0.280
-0.346
0.243
-0.116
0.051
-0.377
0.012
0.039
-0.117
-0.453
-0.509
-0.267
0.551
-0.233
0.244
-0.703
-0.325
-0.334
0.449
-0.230
0.473
0.307
0.309
-0.447
0.316
-0.408
-0.083
-0.590
-0.430
-0.445
-0.083
-
0.185
0.244
Zn
-0.947
-0.581
0.749
0.830
-0.771
0.092
0.449
0.858
-0.633
0.681
0.363
0.945
0.269
0.870
-0.721
0.721
-0.316
0.851
0.944
0.654
-0.654
-0.066
0.272
-0.074
0.059
0.375
0.164
0.630
-0.447
0.811
0.946
0.384
0.464
-0.456
-
0.489
Z
0.416
0.298
-0.386
-0.574
0.203
-0.285
0.345
-0.395
-0.056
-0.058
-0.269
-0.366
-0.358
-0.070
0.453
-0.204
-0.015
-0.386
-0.345
-0.380
0.405
0.031
0.448
-0.302
0.351
-0.366
0.112
-0.435
0.165
-0.487
-0.250
-0.283
-0.102
0.406
-0.248
-
142
d) Fe a a W E plan
FERRARA
G ain size
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
As
Ba
Ce
Cl
Co
C
Cu
Ga
H
La
Mo
Nb
Nd
Ni
Pb
Rb
S
Sc
Sn
S
Th
V
Y
Zn
Z
G ain size
-
0,902
0,602
0,851
0,977
0,770
0,852
0,857
0,888
0,786
0,522
0,894
0,323
0,250
0,276
0,213
0,224
0,270
0,216
0,240
0,364
0,653
0,201
0,209
0,750
0,267
0,383
0,184
0,254
0,141
0,388
0,269
0,361
0,219
0,203
0,350
0,208
SiO2
-0,045
-
1E-06
2E-10
1E-09
1E-07
2E-10
4E-10
8E-06
8E-06
2E-06
1E-09
0,004
0,020
0,014
0,046
0,034
0,013
0,043
0,024
0,043
5E-06
0,063
0,060
0,000
0,014
0,001
0,094
0,019
0,325
0,001
0,014
0,001
0,040
0,095
0,003
0,053
TiO2
-0,189
0,976
-
3E-06
3E-06
8E-08
5E-07
4E-06
0,000
1E-05
5E-07
8E-06
0,001
0,008
0,005
0,020
0,014
0,005
0,018
0,009
0,027
4E-06
0,028
0,027
0,000
0,005
0,000
0,045
0,007
0,191
0,000
0,005
0,000
0,017
0,046
0,001
0,024
Al2O3
-0,068
0,997
0,972
-
8E-08
4E-07
1E-10
2E-15
2E-06
3E-06
6E-07
5E-11
0,003
0,018
0,012
0,041
0,030
0,011
0,038
0,021
0,041
2E-06
0,058
0,054
0,000
0,012
0,001
0,086
0,016
0,306
0,001
0,012
0,001
0,036
0,086
0,002
0,048
Fe2O3
0,010
0,996
0,972
0,988
-
1E-07
1E-08
1E-07
2E-05
1E-05
1E-05
1E-07
0,005
0,024
0,017
0,052
0,039
0,016
0,048
0,028
0,044
1E-05
0,070
0,067
0,000
0,017
0,002
0,104
0,022
0,344
0,002
0,016
0,001
0,046
0,103
0,003
0,060
MnO
-0,106
0,988
0,988
0,982
0,987
-
1E-07
6E-07
0,000
2E-05
1E-06
1E-06
0,003
0,015
0,011
0,035
0,026
0,010
0,033
0,018
0,038
8E-06
0,048
0,046
0,000
0,010
0,001
0,074
0,014
0,270
0,001
0,010
0,001
0,031
0,075
0,002
0,041
MgO
-0,068
0,998
0,981
0,998
0,992
0,986
-
3E-10
8E-06
9E-07
5E-07
3E-09
0,003
0,018
0,012
0,040
0,030
0,011
0,038
0,021
0,041
3E-06
0,057
0,053
0,000
0,012
0,001
0,085
0,016
0,303
0,001
0,012
0,001
0,035
0,085
0,002
0,047
CaO
-0,066
0,997
0,969
1,000
0,987
0,980
0,997
-
2E-06
3E-06
7E-07
7E-12
0,004
0,020
0,014
0,045
0,034
0,013
0,042
0,023
0,044
4E-06
0,063
0,059
0,000
0,014
0,001
0,093
0,018
0,324
0,001
0,013
0,001
0,040
0,093
0,002
0,053
Na2O
0,051
0,963
0,902
0,973
0,952
0,919
0,963
0,974
-
4E-05
0,000
3E-06
0,006
0,025
0,017
0,052
0,041
0,017
0,049
0,029
0,041
3E-05
0,073
0,067
0,001
0,017
0,002
0,102
0,023
0,333
0,002
0,017
0,002
0,046
0,099
0,004
0,060
K2O
-0,099
0,962
0,960
0,971
0,957
0,953
0,978
0,971
0,945
-
2E-06
6E-06
0,004
0,017
0,012
0,037
0,028
0,011
0,035
0,019
0,043
1E-05
0,052
0,048
0,001
0,011
0,001
0,076
0,015
0,273
0,001
0,011
0,001
0,033
0,073
0,002
0,043
P2O5
-0,230
0,972
0,982
0,981
0,958
0,978
0,981
0,980
0,929
0,976
-
2E-06
0,001
0,008
0,006
0,021
0,015
0,005
0,019
0,010
0,030
2E-06
0,031
0,029
0,001
0,005
0,000
0,048
0,008
0,201
0,000
0,005
0,000
0,018
0,049
0,001
0,025
LOI
-0,049
0,996
0,963
0,998
0,987
0,978
0,995
0,999
0,971
0,965
0,974
-
0,007
0,030
0,021
0,063
0,048
0,020
0,059
0,034
0,061
1E-05
0,086
0,081
0,001
0,021
0,002
0,123
0,027
0,392
0,002
0,020
0,002
0,056
0,124
0,004
0,073
As
-0,349
0,814
0,862
0,823
0,801
0,828
0,823
0,815
0,794
0,820
0,861
0,788
-
9E-08
9E-09
5E-06
1E-06
6E-09
4E-06
2E-07
6E-05
9E-05
2E-05
1E-05
5E-05
8E-09
1E-09
7E-05
6E-08
0,003
4E-09
7E-09
2E-08
3E-06
7E-05
2E-12
9E-06
Ba
-0,402
0,714
0,779
0,725
0,701
0,736
0,726
0,716
0,699
0,730
0,776
0,683
0,988
-
2E-12
3E-09
8E-11
5E-12
1E-09
4E-15
1E-05
0,001
7E-08
4E-08
0,000
2E-12
4E-06
8E-07
9E-18
0,000
5E-06
4E-12
1E-05
6E-10
9E-07
6E-07
1E-08
Ce
-0,382
0,741
0,801
0,752
0,728
0,761
0,752
0,743
0,726
0,755
0,799
0,711
0,993
0,999
-
4E-08
4E-09
9E-17
2E-08
4E-11
1E-05
0,001
4E-07
3E-07
0,000
8E-17
9E-07
3E-06
3E-13
0,001
2E-06
5E-17
3E-06
1E-08
4E-06
1E-07
1E-07
Cl
-0,432
0,641
0,717
0,653
0,629
0,668
0,654
0,643
0,628
0,662
0,712
0,607
0,968
0,995
0,990
-
1E-12
5E-08
8E-18
5E-10
9E-06
0,005
2E-11
2E-12
0,002
4E-08
5E-05
4E-09
5E-09
5E-05
7E-05
5E-08
0,000
2E-15
6E-09
1E-05
1E-14
Co
-0,423
0,670
0,743
0,680
0,657
0,695
0,682
0,670
0,652
0,688
0,737
0,636
0,976
0,998
0,995
0,999
-
5E-09
2E-13
6E-12
9E-06
0,003
8E-10
3E-10
0,001
4E-09
2E-05
5E-08
2E-10
0,000
3E-05
5E-09
5E-05
2E-14
6E-08
5E-06
4E-11
C
-0,387
0,745
0,805
0,756
0,732
0,765
0,756
0,747
0,729
0,758
0,803
0,715
0,994
0,999
1,000
0,990
0,994
-
3E-08
7E-11
2E-05
0,001
5E-07
3E-07
0,000
3E-20
8E-07
4E-06
9E-13
0,001
1E-06
2E-23
2E-06
2E-08
4E-06
7E-08
2E-07
Cu
-0,429
0,648
0,722
0,659
0,635
0,674
0,660
0,649
0,634
0,668
0,718
0,614
0,970
0,996
0,991
1,000
1,000
0,991
-
2E-10
9E-06
0,004
6E-11
8E-12
0,001
3E-08
4E-05
8E-09
3E-09
6E-05
6E-05
3E-08
8E-05
6E-18
1E-08
1E-05
2E-13
Ga
-0,410
0,702
0,769
0,713
0,689
0,725
0,713
0,703
0,686
0,718
0,765
0,670
0,985
1,000
0,998
0,997
0,999
0,998
0,997
-
1E-05
0,002
2E-08
1E-08
0,001
4E-11
6E-06
4E-07
8E-14
0,000
9E-06
6E-11
2E-05
9E-11
5E-07
1E-06
3E-09
H
-0,322
0,648
0,692
0,653
0,646
0,661
0,652
0,644
0,651
0,647
0,682
0,610
0,938
0,960
0,957
0,961
0,962
0,956
0,962
0,960
-
0,005
9E-06
1E-05
0,001
1E-05
2E-04
2E-05
1E-05
0,001
0,000
2E-05
0,000
9E-06
2E-05
1E-04
1E-05
La
-0,163
0,966
0,969
0,972
0,958
0,962
0,972
0,969
0,948
0,958
0,974
0,957
0,931
0,863
0,883
0,809
0,830
0,885
0,814
0,854
0,800
-
0,008
7E-03
1E-05
0,001
1E-05
0,014
0,001
0,089
7E-06
0,001
5E-06
0,004
0,014
4E-05
0,006
Mo
-0,442
0,606
0,688
0,616
0,595
0,636
0,618
0,606
0,589
0,627
0,678
0,568
0,954
0,989
0,982
0,999
0,996
0,981
0,998
0,991
0,961
0,780
-
2E-13
0,003
5E-07
0,000
9E-11
1E-07
2E-05
0,000
5E-07
0,000
1E-10
3E-10
5E-05
8E-13
Nb
-0,435
0,612
0,691
0,624
0,600
0,640
0,625
0,613
0,600
0,637
0,685
0,576
0,957
0,990
0,984
0,999
0,997
0,983
0,999
0,993
0,959
0,787
1,000
-
0,002
3E-07
0,000
1E-10
6E-08
2E-05
0,000
3E-07
0,000
3E-11
2E-10
4E-05
9E-15
Nd
-0,116
0,905
0,911
0,900
0,910
0,909
0,903
0,895
0,881
0,876
0,891
0,876
0,942
0,896
0,910
0,856
0,872
0,912
0,860
0,889
0,886
0,959
0,837
0,840
-
0,000
1E-05
0,005
0,000
0,040
1E-05
0,000
2E-05
0,001
0,0048
3E-05
0,002
Ni
-0,388
0,743
0,803
0,753
0,730
0,763
0,754
0,744
0,726
0,756
0,801
0,713
0,994
0,999
1,000
0,990
0,994
1,000
0,991
0,998
0,957
0,884
0,982
0,984
0,911
-
9E-07
4E-06
4E-13
0,001
1E-06
3E-21
3E-06
2E-08
4E-06
9E-08
1E-07
Pb
-0,310
0,863
0,900
0,872
0,851
0,873
0,871
0,865
0,844
0,865
0,901
0,841
0,996
0,969
0,978
0,940
0,952
0,980
0,943
0,965
0,916
0,960
0,923
0,927
0,958
0,979
-
0,000
3E-06
0,009
2E-16
8E-07
2E-11
4E-05
0,000
1E-11
8E-05
Rb
-0,457
0,557
0,642
0,570
0,545
0,588
0,571
0,559
0,547
0,585
0,636
0,520
0,936
0,979
0,970
0,994
0,990
0,969
0,994
0,983
0,952
0,743
0,998
0,998
0,804
0,970
0,899
-
1E-06
3E-06
0,000
4E-06
0,001
1E-08
3E-13
0,000
7E-10
S
-0,399
0,720
0,784
0,731
0,707
0,742
0,732
0,722
0,705
0,735
0,781
0,689
0,989
1,000
0,999
0,994
0,997
0,999
0,995
1,000
0,959
0,868
0,988
0,989
0,900
0,999
0,972
0,977
-
0,000
4E-06
6E-13
7E-06
1E-09
1E-06
4E-07
2E-08
Sc
-0,501
0,348
0,451
0,361
0,335
0,386
0,363
0,348
0,342
0,384
0,442
0,305
0,827
0,904
0,886
0,942
0,929
0,883
0,939
0,911
0,891
0,565
0,956
0,954
0,654
0,885
0,771
0,972
0,900
-
0,010
0,001
0,012
7E-05
3E-06
0,005
3E-05
Sn
-0,307
0,869
0,905
0,878
0,857
0,879
0,877
0,872
0,850
0,870
0,907
0,848
0,994
0,966
0,976
0,936
0,948
0,977
0,939
0,961
0,912
0,964
0,918
0,922
0,960
0,976
1,000
0,894
0,968
0,763
-
1E-06
5E-12
5E-05
0,001
9E-11
0,000
S
-0,387
0,744
0,804
0,754
0,731
0,764
0,755
0,746
0,728
0,757
0,802
0,714
0,994
0,999
1,000
0,990
0,994
1,000
0,991
0,998
0,956
0,885
0,982
0,984
0,911
1,000
0,979
0,969
0,999
0,884
0,977
-
3E-06
2E-08
4E-06
8E-08
1E-07
Th
-0,324
0,876
0,916
0,885
0,862
0,887
0,885
0,879
0,850
0,878
0,917
0,856
0,992
0,961
0,971
0,929
0,942
0,972
0,932
0,956
0,897
0,966
0,911
0,914
0,953
0,972
0,999
0,885
0,963
0,752
0,999
0,972
-
7E-05
0,001
1E-09
0,000
V
-0,427
0,654
0,728
0,666
0,641
0,680
0,666
0,656
0,640
0,674
0,723
0,620
0,972
0,997
0,992
1,000
1,000
0,992
1,000
0,998
0,962
0,819
0,998
0,998
0,863
0,992
0,946
0,993
0,996
0,936
0,941
0,992
0,93522
-
2E-08
9E-06
1E-12
Y
-0,441
0,557
0,640
0,569
0,546
0,587
0,571
0,558
0,550
0,589
0,635
0,519
0,935
0,978
0,970
0,994
0,989
0,968
0,993
0,982
0,955
0,744
0,997
0,997
0,807
0,969
0,899
0,999
0,977
0,971
0,893
0,969
0,88388
0,99
-
0,0002
1E-09
Zn
-0,331
0,836
0,879
0,845
0,823
0,848
0,845
0,838
0,818
0,841
0,879
0,812
0,999
0,981
0,988
0,957
0,967
0,989
0,959
0,977
0,930
0,945
0,941
0,945
0,950
0,988
0,999
0,921
0,983
0,803
0,998
0,988
0,99578
0,96
0,920
-
3E-05
Z
-0,436
0,625
0,702
0,637
0,612
0,652
0,638
0,626
0,612
0,647
0,697
0,590
0,962
0,993
0,987
1,000
0,998
0,986
1,000
0,995
0,961
0,796
0,999
1,000
0,846
0,987
0,933
0,996
0,992
0,949
0,928
0,986
0,92111
1,00
0,996
0,95021
-
143
e) Fo lì W E plan
FORLÌ
G ain size
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
As
Ba
Ce
Cl
Co
C
Cu
Ga
H
La
Mo
Nb
Nd
Ni
Pb
Rb
S
Sc
Sn
S
Th
V
Y
Zn
Z
G ain size
-
2E-05
0,696
0,225
0,0424
0,209
0,338
0,001
0,025
0,029
0,230
0,000
0,113
0,887
0,016
0,271
0,008
0,228
0,053
0,157
0,814
0,347
0,137
0,192
0,416
0,091
0,157
0,031
0,0052
0,208
4E-05
4E-05
0,097
0,675
0,698
0,000
0,006
SiO2
0,969
-
0,655
0,190
0,0443
0,153
0,273
0,000
0,022
0,011
0,201
0,000
0,080
0,815
0,012
0,179
0,024
0,175
0,014
0,117
0,722
0,371
0,087
0,150
0,465
0,180
0,111
0,013
0,0011
0,326
1E-06
1E-05
0,053
0,653
0,687
0,001
0,002
TiO2
-0,152
-0,173
-
0,497
0,1059
0,001
0,113
0,173
0,072
0,921
0,001
0,481
0,006
4E-06
0,138
0,571
0,620
0,000
0,776
0,002
0,206
0,206
0,008
0,081
0,233
0,513
0,008
0,031
0,1927
0,725
0,477
0,775
0,019
0,003
6E-06
0,297
0,734
Al2O3
0,449
0,481
0,261
-
0,0670
0,919
0,100
0,334
0,830
0,002
0,806
0,447
0,831
0,638
0,947
0,873
0,718
0,913
0,213
0,731
0,499
0,487
0,519
0,015
0,569
0,820
0,842
0,434
0,3658
0,112
0,247
0,158
0,707
0,233
0,581
0,712
0,209
Fe2O3
0,683
0,679
0,574
0,634
-
0,609
0,006
0,276
0,832
0,033
0,516
0,153
0,868
0,084
0,536
0,580
0,318
0,487
0,088
0,700
0,405
0,872
0,878
0,001
0,973
0,646
0,837
0,741
0,2869
0,637
0,104
0,046
0,936
0,009
0,119
0,254
0,011
MnO
0,464
0,518
-0,894
-0,040
-0,1983
-
0,621
0,011
0,022
0,434
0,000
0,134
1E-06
0,003
0,009
0,256
0,443
2E-06
0,626
0,000
0,207
0,191
0,001
0,473
0,165
0,522
6E-06
0,001
0,0108
0,678
0,101
0,274
5E-05
0,112
0,001
0,059
0,469
MgO
0,362
0,410
0,564
0,583
0,8289
-0,192
-
0,557
0,492
0,060
0,506
0,720
0,861
0,166
0,760
0,808
0,761
0,400
0,372
0,665
0,963
0,880
0,830
0,011
0,850
0,899
0,956
0,942
0,5009
0,756
0,484
0,430
0,882
0,001
0,153
0,824
0,046
CaO
-0,897
-0,926
0,498
-0,365
-0,4080
-0,789
-0,227
-
0,005
0,033
0,017
0,001
0,003
0,245
0,001
0,151
0,063
0,016
0,085
0,007
0,743
0,233
0,008
0,480
0,253
0,195
0,006
0,000
9E-06
0,285
0,000
0,003
0,002
0,797
0,168
0,000
0,021
Na2O
0,731
0,742
-0,625
0,084
0,0832
0,741
-0,264
-0,836
-
0,332
0,023
0,002
0,021
0,171
0,008
0,080
0,018
0,010
0,100
0,019
0,706
0,199
0,037
0,971
0,747
0,171
0,049
0,007
0,0070
0,157
0,004
0,016
0,040
0,233
0,097
0,001
0,186
K2O
0,718
0,791
0,039
0,879
0,7080
0,299
0,647
-0,707
0,367
-
0,560
0,083
0,253
0,999
0,239
0,519
0,365
0,488
0,043
0,252
0,758
0,990
0,152
0,028
0,346
0,534
0,259
0,069
0,0409
0,247
0,024
0,019
0,157
0,310
0,981
0,168
0,019
P2O5
-0,445
-0,470
0,914
0,096
0,2504
-0,991
0,256
0,760
-0,740
-0,225
-
0,154
8E-06
0,002
0,009
0,306
0,414
4E-06
0,769
3E-05
0,161
0,178
0,002
0,366
0,163
0,453
0,000
0,002
0,0200
0,593
0,129
0,330
0,000
0,082
0,000
0,065
0,554
LOI
-0,940
-0,947
0,271
-0,291
-0,5180
-0,540
-0,140
0,893
-0,875
-0,607
0,517
-
0,083
0,708
0,007
0,162
0,002
0,121
0,014
0,109
0,578
0,348
0,120
0,367
0,627
0,126
0,133
0,018
0,0038
0,225
5E-06
4E-05
0,077
0,952
0,518
0,000
0,014
As
0,565
0,612
-0,828
0,084
-0,0648
0,986
-0,069
-0,858
0,745
0,426
-0,975
-0,608
-
0,009
0,004
0,289
0,358
0,000
0,503
3E-06
0,199
0,231
0,000
0,673
0,110
0,443
0,000
0,000
0,0040
0,550
0,052
0,171
2E-06
0,212
0,004
0,036
0,303
Ba
-0,056
-0,091
0,979
0,183
0,6062
-0,865
0,505
0,433
-0,499
0,000
0,878
0,146
-0,805
-
0,233
0,760
0,901
0,001
0,640
0,003
0,131
0,308
0,007
0,084
0,160
0,654
0,008
0,043
0,2687
0,781
0,648
0,973
0,022
0,006
0,000
0,503
0,619
Ce
0,766
0,788
-0,535
0,026
0,2387
0,803
0,119
-0,906
0,813
0,437
-0,801
-0,821
0,844
-0,443
-
0,109
0,110
0,017
0,149
0,015
0,538
0,113
0,052
0,865
0,493
0,211
0,007
0,006
0,0010
0,523
0,006
0,041
0,005
0,705
0,121
0,001
0,030
Cl
-0,412
-0,492
0,219
-0,063
-0,2141
-0,423
-0,095
0,521
-0,612
-0,249
0,385
0,509
-0,398
0,119
-0,570
-
0,652
0,281
0,161
0,387
0,379
0,203
0,427
0,325
0,229
0,994
0,358
0,242
0,0461
0,643
0,134
0,208
0,331
0,947
0,680
0,128
0,146
Co
-0,811
-0,734
0,192
-0,141
-0,3762
-0,294
0,119
0,641
-0,759
-0,344
0,312
0,871
-0,349
0,049
-0,569
0,175
-
0,337
0,115
0,347
0,465
0,447
0,360
0,746
0,635
0,027
0,489
0,167
0,1530
0,169
0,013
0,006
0,396
0,694
0,685
0,005
0,175
C
0,447
0,496
-0,931
-0,043
-0,2675
0,984
-0,321
-0,765
0,798
0,267
-0,979
-0,555
0,960
-0,893
0,762
-0,404
-0,363
-
0,591
8E-06
0,328
0,202
0,000
0,394
0,202
0,434
0,000
0,001
0,0185
0,524
0,103
0,259
0,001
0,049
0,000
0,060
0,585
Cu
0,660
0,775
0,111
0,460
0,5990
0,189
0,339
-0,604
0,582
0,682
-0,115
-0,776
0,258
0,182
0,522
-0,509
-0,563
0,208
-
0,535
0,113
0,878
0,509
0,082
0,682
0,567
0,587
0,179
0,0701
0,419
0,013
0,009
0,391
0,461
0,718
0,057
0,010
Ga
0,514
0,560
-0,871
0,134
-0,1500
0,973
-0,168
-0,819
0,752
0,427
-0,964
-0,571
0,982
-0,861
0,771
-0,329
-0,356
0,975
0,240
-
0,251
0,284
0,000
0,584
0,099
0,394
1E-05
0,000
0,0111
0,397
0,072
0,199
6E-05
0,121
0,001
0,062
0,439
H
0,092
0,139
0,466
0,260
0,3179
-0,465
-0,018
0,128
0,147
0,120
0,509
-0,215
-0,472
0,543
-0,238
-0,334
-0,281
-0,369
0,565
-0,428
-
0,729
0,372
0,165
0,038
0,978
0,128
0,560
0,8501
0,501
0,677
0,415
0,207
0,524
0,113
0,880
0,658
La
0,356
0,340
-0,466
-0,267
-0,0631
0,480
-0,059
-0,443
0,473
-0,005
-0,492
-0,355
0,444
-0,383
0,565
-0,469
-0,291
0,470
0,060
0,402
-0,135
-
0,257
0,676
0,797
0,052
0,249
0,270
0,2302
0,835
0,331
0,525
0,283
0,567
0,342
0,192
0,385
Mo
0,536
0,600
-0,814
0,249
-0,0601
0,915
-0,084
-0,809
0,698
0,520
-0,879
-0,556
0,925
-0,817
0,662
-0,304
-0,347
0,920
0,254
0,951
-0,339
0,422
-
0,772
0,079
0,371
0,001
9E-05
0,0125
0,526
0,067
0,151
0,000
0,172
0,012
0,081
0,444
Nb
0,479
0,521
0,610
0,772
0,8911
-0,276
0,791
-0,271
0,014
0,721
0,343
-0,343
-0,164
0,606
0,067
-0,372
-0,126
-0,325
0,608
-0,212
0,506
-0,163
-0,113
-
0,554
0,915
0,642
0,902
0,3864
0,451
0,236
0,132
0,832
0,009
0,089
0,578
0,041
Nd
-0,310
-0,280
0,442
-0,220
-0,0131
-0,505
-0,074
0,426
-0,126
-0,356
0,507
0,189
-0,568
0,511
-0,264
-0,446
0,184
-0,469
0,159
-0,583
0,695
0,100
-0,614
0,228
-
0,654
0,087
0,148
0,4389
0,859
0,528
0,603
0,083
0,503
0,157
0,551
0,979
Ni
-0,595
-0,490
0,252
-0,089
-0,1784
-0,247
0,050
0,476
-0,500
-0,240
0,288
0,549
-0,294
0,174
-0,462
-0,003
0,727
-0,299
-0,222
-0,325
-0,011
-0,662
-0,340
0,042
0,174
-
0,505
0,304
0,3942
0,321
0,149
0,168
0,508
0,711
0,598
0,118
0,308
Pb
0,514
0,567
-0,814
0,078
-0,0806
0,977
-0,022
-0,824
0,669
0,421
-0,964
-0,540
0,993
-0,809
0,821
-0,348
-0,266
0,938
0,211
0,971
-0,547
0,429
0,911
-0,181
-0,600
-0,257
-
0,000
0,0076
0,662
0,084
0,243
1E-06
0,250
0,004
0,065
0,324
Rb
0,712
0,779
-0,712
0,299
0,1291
0,911
0,028
-0,937
0,822
0,630
-0,874
-0,757
0,947
-0,682
0,829
-0,435
-0,504
0,908
0,491
0,947
-0,225
0,412
0,949
0,048
-0,524
-0,386
0,923
-
0,0005
0,374
0,007
0,034
6E-05
0,349
0,034
0,012
0,142
S
-0,834
-0,896
0,478
-0,343
-0,3994
-0,793
-0,259
0,974
-0,819
-0,687
0,750
0,849
-0,847
0,413
-0,897
0,675
0,518
-0,756
-0,628
-0,791
0,074
-0,445
-0,783
-0,330
0,296
0,325
-0,814
-0,915
-
0,386
0,001
0,007
0,003
0,877
0,198
0,002
0,018
Sc
0,464
0,371
-0,137
0,566
0,1834
0,161
-0,121
-0,401
0,513
0,431
-0,207
-0,449
0,231
-0,108
0,246
-0,180
-0,501
0,245
0,309
0,323
0,259
-0,082
0,244
0,289
-0,069
-0,374
0,170
0,338
-0,330
-
0,207
0,179
0,719
0,740
0,580
0,336
0,564
Sn
-0,961
-0,985
0,273
-0,431
-0,5762
-0,580
-0,269
0,945
-0,841
-0,737
0,545
0,978
-0,661
0,177
-0,830
0,540
0,783
-0,579
-0,779
-0,625
-0,162
-0,367
-0,634
-0,440
0,244
0,522
-0,606
-0,817
0,914
-0,465
-
1E-05
0,042
0,906
0,502
0,000
0,005
S
-0,959
-0,971
0,112
-0,513
-0,6762
-0,409
-0,302
0,859
-0,767
-0,755
0,368
0,960
-0,500
0,013
-0,686
0,464
0,824
-0,421
-0,805
-0,472
-0,311
-0,245
-0,520
-0,542
0,202
0,503
-0,434
-0,705
0,817
-0,492
0,973
-
0,141
0,723
0,824
0,001
0,009
Th
0,587
0,660
-0,753
0,146
0,0314
0,958
0,058
-0,871
0,689
0,514
-0,926
-0,616
0,984
-0,744
0,832
-0,367
-0,323
0,917
0,326
0,955
-0,465
0,402
0,927
-0,083
-0,607
-0,255
0,986
0,955
-0,863
0,140
-0,683
-0,532
-
0,347
0,016
0,039
0,216
V
0,163
0,175
0,860
0,443
0,8067
-0,567
0,894
0,101
-0,443
0,382
0,609
0,023
-0,461
0,829
-0,147
-0,026
0,153
-0,668
0,283
-0,555
0,246
-0,221
-0,499
0,804
0,258
0,144
-0,429
-0,355
0,060
-0,130
-0,046
-0,138
-0,356
-
0,007
0,783
0,151
Y
-0,151
-0,157
0,977
0,214
0,5571
-0,895
0,519
0,502
-0,587
0,009
0,928
0,249
-0,848
0,971
-0,555
0,160
0,158
-0,920
0,141
-0,888
0,564
-0,360
-0,786
0,597
0,514
0,204
-0,844
-0,705
0,473
-0,214
0,259
0,087
-0,768
0,818
-
0,329
0,755
Zn
-0,922
-0,915
0,392
-0,144
-0,4251
-0,647
-0,087
0,917
-0,894
-0,503
0,636
0,975
-0,699
0,258
-0,895
0,546
0,833
-0,646
-0,652
-0,642
-0,059
-0,479
-0,609
-0,215
0,231
0,559
-0,637
-0,789
0,880
-0,363
0,951
0,898
-0,693
0,107
0,369
-
0,024
Z
0,827
0,877
0,132
0,463
0,7944
0,278
0,675
-0,747
0,485
0,753
-0,229
-0,776
0,387
0,193
0,718
-0,526
-0,496
0,212
0,796
0,296
0,172
0,330
0,293
0,687
-0,010
-0,384
0,372
0,531
-0,758
0,223
-0,832
-0,805
0,458
0,521
0,122
-0,735
-
144
APPENDIX VIII
XRF esul s analysed by PCA o 5 W E in es iga ed.
a) Pa ma W E plan

145
b) Piacenza W E plan
146
c) To ino W E plan
147
d) Fe a a W E plan
148
e) Fo lì W E plan s