Miner Petrol
DOI 10.1007/s00710-016-0485-8
ORIGINAL PAPER
Effects of limestone petrography and calcite microstructure
on OPC clinker raw meals burnability
Matteo Galimberti 1 & Nicoletta Marinoni 1 & Giovanna Della Porta 1 &
Maurizio Marchi 2 & Monica Dapiaggi 1
Received: 19 September 2016 / Accepted: 22 November 2016
# Springer-Verlag Wien 2016
Abstract Limestone represents the main raw material for or-
dinary Portland cement clinker production. In this study eight
natural limestones from different geological environments
were chosen to prepare raw meals for clinker manufacturing,
aiming to define a parameter controlling the burnability. First,
limestones were characterized by X-Ray Fluorescence, X-Ray
Powder Diffraction and Optical Microscopy to assess their
suitability for clinker production and their petrographic fea-
tures. The average domains size and the microstrain of calcite
were also determined by X-Ray Powder Diffraction line pro-
file analysis. Then, each limestone was admixed with clay
minerals to achieve the adequate chemical composition for
clinker production. Raw meals were thermally threated at sev-
en different temperatures, from 1000 to 1450 °C, to evaluate
their behaviour on heating by ex situ X-Ray Powder
Diffraction and to observe the final clinker morphology by
Scanning Electron Microscopy. Results indicate the calcite
microstrain is a reliable parameter to predict the burnability
of the raw meals, in terms of calcium silicates growth and lime
consumption. In particular, mixtures prepared starting from
high-strained calcite exhibit a better burnability. Later, when
the melt appears this correlation vanishes; however differ-
ences in the early burnability still reflect on the final clinker
composition and texture.
Editorial handling: D. Paktunc
* Matteo Galimberti
Matteo.galimberti@unimi.it
1
Dipartimento di Scienze della Terra BArdito Desio^, Università degli
Studi di Milano, via Botticelli 23, 20133 Milan, Italy
2
Italcementi S.p.A., via Camozzi 124, 24121 Bergamo, Italy
Keywords Limestone . Calcite . Clinker . Cement . X-ray
powder diffraction
Introduction
Ordinary Portland cement (OPC) clinker is made by heating at
1450 °C in a rotary kiln a fine-grained mixture of limestone
and clay minerals in a ratio ranging from 4:1 to 5:1 by mass,
through a highly energy-intensive process. First, the decom-
position of clay minerals and the dissociation of carbonates
happen, then at higher temperatures a partial fusion occurs and
nodules of clinker form (Taylor 1990). Besides exhaust gases
released by kiln fuels, calcination itself contributes to the 5%
by mass to the global anthropogenic carbon dioxide emis-
sions, raising the volume of greenhouse gases in the atmo-
sphere (Van Oss and Padovani 2002). Accordingly, a better
comprehension of the whole clinkerization process in terms of
raw meal burnability is an attractive approach for energy pres-
ervation, greenhouse gases abatement, costs reduction and
kiln output increase, which are the main aims of modern ce-
ment industry (Snellings et al. 2012; Puerta-Falla et al. 2015).
The term Bburnability^ of an OPC clinker raw meal refers (i)
to the way the carbonates, mostly calcite, decompose upon
heating and (ii) to the manner the resulting CaO reacts with
SiO2, Al2O3 and Fe2O3 to form the clinker crystalline
phases. A raw meal exhibits a good burnability when
the carbonates decompose at low temperature through a
fast-rate reaction and lead to a clinker with high content
of calcium silicates and free lime not exceeding the 5% by
mass (Ghosh and Kurdowski 1991).
The various aspects of calcination have been widely inves-
tigated; several authors clarified the kinetic mechanisms driv-
ing it (Lech 2006c; Rodriguez-Navarro et al. 2009; Beruto
et al. 2010), whereas others focused on how the limestone

features influence the carbonate thermal decomposition dur-
ing clinker and lime production (Moropoulou et al. 2001;
Lech 2006a, b; Lech et al. 2009; Soltan et al. 2011, 2012;
Alaabed et al. 2014). These studies indicate that a limestone
has not be considered as a mere assemblage of carbonate
minerals. Attention should be paid to its mineralogy and
microfabric too, both factors strongly affecting the ther-
mal behaviour. For instance, the presence of dolomite also
speeds the calcite decomposition (Marinoni et al. 2012a),
whereas limestone microfabric influences both the crystal-
lization temperature of the clinker phases and the free
lime content in the final product (Marinoni et al. 2015).
On the other hand, the influence of the physical-chemical
features of the starting materials on the clinkerization is
still modestly investigated.
Hence, this study aims to investigate, for the first time, how
the limestone microfabric (texture, components grain size)
and the calcite microstructure (average domains size and
microstrain) jointly affect the clinkerization, by combining
ex situ X-Ray Powder Diffraction (XRPD) and Scanning
Electron Microscopy (SEM) analyses. Microstructure is a
term encompassing the compositional inhomogeneity and
the magnitude of defects within a crystal lattice; these features
control the characteristics of a material such as its reactivity
and technical properties (Scardi and Leoni 2006; Marinoni
et al. 2012b; Marinoni and Broekmans 2013; Jayasankar
et al. 2016). In such a light, eight different limestone samples
were selected and characterized by mineralogical, chemical
and optical microscopy analyses. Eight laboratory OPC clin-
ker raw meals with fixed chemical composition were prepared
by mixing each limestone with clay minerals and iron oxides
and then thermally treated, at different temperatures, in a lab-
oratory furnace to simulate the industrial process. Sintered
clinkers have been analysed by ex situ XRPD and SEM, to
gather information on the crystallization temperature of main
clinker phases, their weight fraction, morphology and
distribution.
In this paper chemical formulae are expressed as a sum of
oxides, complying with the abbreviations used by cement
chemistry scientists (e.g. C = CaO, S = SiO2, A = Al2O3,
F = Fe2O3); nevertheless, simple oxide phases are written in
full, according to the standard notation (e.g. periclase will be
MgO and not only M).
Materials
Eight carbonate rock samples, labelled as SA, SL, UM, MO1,
MO2, MO3, MO4 and AS, were selected as starting materials.
To ensure textural variability, they cover a wide array of car-
bonate microfacies and comprise all the categories of the
Dunham’s classification (Dunham 1962). Moreover, to avoid
effects due to impurities during the thermal treatment, only
limestones with a level of calcite higher than 98% by mass
M. Galimberti et al.
and a negligible content of minor and trace elements were
considered. These requirements made necessary to space
widely in terms of outcrop location and age.
The SA calcite cement crust is a fossil karstic cave filling of
undetermined age, probably Quaternary, developed within the
Upper Jurassic limestone of north-eastern Sardinia (Italy), as a
result of meteoric vadose and phreatic diagenesis due to the
limestone subaerial exposure. Sample SL derives from the
Lower Eocene (Ypresian) Alveolina-Nummulites Limestone
cropping out in the Kras Plateau (SW Slovenia), which be-
longs to the Komen Thrust Unit of the NW External Dinarides
fold-and-thrust belt. During the Late Cretaceous and
Paleogene, shallow-water carbonate accumulations developed
on the marginal areas of a vast Mesozoic carbonate deposi-
tional system (the Adriatic Carbonate Platform). The Lower
Eocene Alveolina-Nummulites Limestone succession repre-
sents a protected inner ramp with muddy to grainy carbonate
substrates close to seagrass beds (Zamagni et al. 2008). UM is
an Upper Cretaceous (Cenomanian) pelagic limestone from
the Scaglia Bianca Formation, in the Umbria-Marche Basin
(Umbria-Marche Apennines, central Italy), settled in a pelagic
environment at a paleo-depth of 1000–1500 m on the passive
southern margin of the Tethys Ocean (Arthur and Fischer
1977; Premoli Silva and Sliter 1995). Samples MO1, MO2,
MO3 and MO4 are from the Djebel Bou Dahar (DBD)
Mountain in the High Atlas range in central-eastern
Morocco. The DBD carbonate platform developed on
the footwall high of an active marine rift during the
Early Jurassic (Merino-Tomé et al. 2012). The deposition-
al system evolved from a low-angle ramp into a high-
relief platform, with a shallow subtidal to supratidal top
and steep slopes, with coral-microbial reefs developing at
its margin during the Pliensbachian (Verwer et al. 2009;
Della Porta et al. 2013). The AS limestone was sampled
on the Sierra del Cuera (Cantabrian Mountains, Asturias,
northern Spain). During the Pennsylvanian (Bashkirian-
Moscovian), the Cantabrian zone represented the marine
foreland basin of the Variscan Orogen (Bahamonde et al.
2015). High-relief progradational carbonate platforms
with steep slopes dominated by microbialites, such as
the Sierra del Cuera, developed in the distal part of the
Cantabrian foreland basin (Della Porta et al. 2003).
Experimental procedure
Optical microscopy
The limestones were examined by Laboval-3 optical micro-
scope in transmitted plane- (PPL) and cross-polarized light
(XPL) to perform a semi-quantitative analysis of the
microfacies components (texture, matrix composition and
grain types). Micrographs were simultaneously acquired by
Effects of limestone petrography and calcite microstructure

Table 1 Mineralogical
composition (wt%) of limestones Limestone sample SA SL UM MO1 MO2 MO3 MO4 AS
obtained by Rietveld refinements
Calcite 99.8(1) 99.7(1) 99.3(2) 99.9(1) 99.5(2) 99.6(1) 99.7(1) 98.3(2)
Quartz 0.2(1) 0.3(1) 0.7(2) 0.1(1) 0.5(2) 0.4(1) 0.3(1) 0.4(1)
Dolomite b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. b.d.l. 1.3(2)

b.d.l. = below the XRPD detection limit

Nikon Coolpix 990 digital camera at 1.2 megapixel.
Limestone samples were categorized according to the classi-
fication of depositional textures of carbonate rocks proposed
by Dunham (1962) and integrated by Embry and Klovan
(1971).
X-ray fluorescence and X-ray powder diffraction
Pulverized limestones were preliminary dried at 105 °C to
remove non-stoichiometric CO2 and H2O and attain a
constant weight. Their bulk chemical composition was
then determined by wavelength dispersive X-ray fluores-
cence (WD-XRF), operating at 50 kV and 80 mA. The
lowest threshold detection limit was 0.01 wt% for each
elemental species and the data resolution gradually dete-
riorated towards the limit. Loss on ignition was assessed
gravimetrically weighing the samples before and after a
20-min thermal treatment at 1000 °C.
Qualitative phase analyses on both the limestones and
the clinkers were provided by ex situ XRPD experi-
ments, carried out by a ϑ-2ϑ Bragg-Brentano geometry
diffractometer (PANalytical X’Pert Pro), using Cu-Kα
radiation (λ = 1.5418 Å), equipped with multi-channel
X’Celerator detector. Patterns were collected over the
5–80° 2ϑ angular range, with a step size of 0.02° 2ϑ
and a counting time of 30 s/step. Quantitative phase
analyses were performed by the full profile Rietveld
Method implemented in the TOPAS-Academic 5.1 soft-
ware (Young 1993; Coelho 2012).
Calcite microstructural analysis by XRPD
To determine the calcite microstructural features within
powdered limestones, XRPD data were collected by a ϑ-
2ϑ Bragg-Brentano geometry diffractometer (PANalytical
X’Pert Pro), operating at 40 kV and 40 mA, using Cu-Kα
radiation, in the 5–80° 2ϑ range, with a step size of
0.008° 2ϑ and a 30 s/step counting time. The patterns
were then processed by the MAUD software (Ferrari and
Lutterotti 1994), which enables full-profile Rietveld struc-
tural refinement as well as the assessment of the micro-
structure regarding the average crystallites, or domains,
size and the root mean square microstrain, hereafter ad-
dressed simply as domains size and microstrain respec-
tively. Domains are coherently diffracting regions within
a crystal, whereas microstrain is a dimensionless parame-
ter that indicates the magnitude of dislocations, vacancies,
defects and chemical impurities affecting the crystal struc-
ture (Mittemeijer and Scardi 2004). Their contribution to
the diffraction peak broadening is modelled deconvolving
the instrumental component g(x) from the experimental
pattern f(x) and then separating the domains and the
microstrain contributions. For this purpose, an XRPD pat-
tern of a defect-free external standard (NIST SRM 660a
LaB6) had been previously acquired, to determine the in-
strumental contribution. Data were then processed follow-
ing the principles outlined in Stokes and Wilson (1942)
and in Warren and Averbach (1952), refining the instru-
mental parameters by adopting an iterative least square
minimization procedure.

Table 2 Bulk chemical composition (wt%) of the limestones, as determined by WD-XRF

Limestone SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O Na2O TiO2 P2O5 Mn2O L.o.I.* Total

SA 0.32 0.17 0.07 54.6 0.06 < 0.01 0.02 < 0.01 0.01 0.11 < 0.01 44.0 99.4
SL 0.01 < 0.01 0.01 54.7 0.46 0.04 < 0.01 < 0.01 0.01 0.01 < 0.01 44.1 99.4
UM 0.58 0.17 0.05 54.2 0.26 0.08 0.05 0.07 0.02 0.08 0.02 43.8 99.4
MO1 0.09 0.02 0.03 55.3 0.22 0.03 < 0.01 < 0.01 0.01 0.02 0.01 44.0 99.7
MO2 0.70 0.21 0.10 53.7 0.51 0.06 0.05 < 0.01 0.02 0.05 0.01 43.9 99.3
MO3 0.31 0.09 0.05 55.3 0.33 0.05 < 0.01 < 0.01 0.01 0.01 0.01 44.0 100.2
MO4 0.50 0.25 0.10 53.7 0.68 0.08 0.06 < 0.01 0.02 0.05 0.01 43.9 99.4
AS 1.54 0.87 0.30 53.4 1.03 0.13 0.16 0.02 0.03 0.02 0.03 42.9 100.4

*L.o.I. = loss on ignition

 M. Galimberti et al.

Fig. 1 Optical micrographs of

the investigated limestones-1. a
SA limestone framework of
sparite crystals (C) and detrital
silt-size sediment (D) filling the
intercrystalline porosity. b SA
limestone close-up of the detrital
sediment (D) between calcite
crystals (C). c SL limestone skel-
etal peloidal packstone with
Alveolina (A), Nummulites (N)
foraminifers and fragments of
echinoderms (E). d SL limestone
micrite (mc) and sparite (sp) as
matrix and as filling of the cham-
bers of an Alveolina (A). e UM
limestone skeletal wackestone to
mudstone with micrite (mc) ma-
trix and scattered planktonic for-
aminifers (F). f AS limestone –
microfacies A skeletal
wackestone/floatstone with a red
micrite matrix (mc) rich in iron
and manganese oxides.
Fragments of crinoids (CR),
fenestellid bryozoans (BR) and
brachiopods (BA). g AS limestone
– microfacies B skeletal
grainstone where micrite was re-
moved by dissolution and sparite
(sp) precipitated in the interparti-
cle space. Bioclasts are crinoids
(CR), benthic foraminifers as
Tetrataxis (F), bryozoans (BR)
and brachiopods (BA) with
geopetal sediment filling indica-
tive of the stratigraphic way-up. h
AS limestone – microfacies C
biocementstone with radiaxial fi-
brous calcite (fc) embedding
fenestellid bryozoans (BR)

Burnability test
This test is intended to simulate the conditions occurring
in the industrial kiln. Each limestone was finely ground
below 80 μm in a jaw crusher and then mixed in different
proportions with clay minerals, silicon oxide and iron ox-
ide to obtain raw meals fitting the optimal chemical com-
position for clinker production. Raw meals were later pel-
letized using a hydraulic press. Lime saturation factor
(LSF = 97.00), silica ratio (SR = 2.50) and alumina ratio
(AR = 1.50) values were kept fixed, to have comparable
raw meals. Pellets were thermally threated at 1000, 1100,
1200, 1300, 1350, 1400 and 1450 °C in an electrical tube
furnace, with a soaking time of 20 min per temperature.
At each step a pellet was drawn from the furnace and
quenched by an air flow. Ex situ XRPD patterns were
then collected and processed under the conditions previ-
ously reported. The obtained clinkers will be hereafter
addressed as clinker_x where x refers to the limestone
used in the raw meal (e.g. clinker _AS refers to the clinker
Effects of limestone petrography and calcite microstructure

Fig. 2 Optical micrographs of

the investigated limestones-2. a
MO1 limestone primary reef
cavity filled by isopachous rims
of radiaxial fibrous calcite (fc)
and equant blocky sparite (bs),
due to early marine and late burial
diagenesis, respectively. Image in
XPL. b MO1 limestone coral (C)
boundstone and peloidal
packstone with laminated
microbialites (M). c MO2 lime-
stone peloidal skeletal packstone
to grainstone with oncoids (O)
and fragments of bivalves (B). d
MO2 limestone cavity filled by
equant blocky sparite (bs)
surrounded by peloids (P) and
textularid foraminifer (F). Image
in XPL. e MO3 limestone peloidal
packstone with gastropod (G) and
fenestral voids (Fe) filled by
sparite cement. f MO3 limestone
with the alga Thaumatoporella
parvovesiculifera (T), foraminifer
(F) and cavity filled by an early
marine (em) and a late burial (lb)
cement. g MO4 limestone coated
grain peloidal packstone and
grainstone with interpaticle pore
space filled by several generations
of calcite cement and micrite
crusts. h MO4 limestone close-up
view of pendant cement (pc) and
laminated micritic crusts (mc) due
to vadose diagenesis. Isopachous
rims of fibrous calcite (fc) and
equant blocky sparite (bs) at fill-
ing the pores, due to early marine
and late burial diagenesis, respec-
tively. Image in XPL

obtained after the burning of the raw meal where the Results
limestone AS represents the carbonate fraction).
Mineralogical and chemical composition of limestones
Scanning electron microscopy by XRPD and XRF

Polished sections of the clinker samples obtained at 1450 °C
throughout the burnability test were also investigated by scan-
ning electron microscopy to understand the morphology and
the spatial distribution of the phases. Backscattered electrons
images were collected under an acceleration current of 15 kV,
a 100 nm beam size and a 11 mm working distance.
All the investigated limestones consist of calcite and traces of
quartz. Dolomite occurs as an accessory phase in the AS sam-
ple only, in negligible amount. The mineralogical similarity
(Table 1) agrees with the results of the chemical analyses
(Table 2), where CaO is the main constituent (53.4–
55.3 wt%), followed by minor amounts of silicon, magnesium
Table 3 Textural features and grain composition of the limestones, as determined by optical microscopy. Samples are listed from younger to older

Sample/ Location/ Age Microfacies Texture (according to Components Diagenetic features Depositional environment
types (if more Dunham and Embry &
than one present) Klovan)

SA/ NE Sardinia (Italy)/ (Fig. 1a-b) Crystalline Porosity between the calcite crystals Prismatic calcite crystals (1–5 mm in cross Filling of karstic cave developed
Quaternary carbonate/sparstone framework, partially filled by section, 5–12 cm in length) within a Jurassic marine
silt-grade fragments of sparite Dissolution processes and erosion of calcite limestone, when subaerially
crystals, crystals forming a detrital silt partially exposed to vadose and phreatic
iron oxides and clay minerals. filling the intercrystalline porosity meteoric diagenesis
Complete lack of bioclasts
SL/ Kras Region, SW (Fig. 1c-d) Skeletal peloidal packstone, Large benthic foraminifers (dominant Shell breakage and sutured grain contact Protected inner ramp
Slovenia/ Eocene with micrite matrix Alveolina, sparse Nummulites, (mechanical and chemical compaction
(Ypresian) Assilina, miliolids, rotalids), with pressure solution during burial
fragments of echinoderms diagenesis)
Peloids (size from 20 to 400 μm) Microsparite precipitation within the
Alveolinid intraparticle pores
Millimetre-size irregular dissolution vugs in
the interparticle space and within
Alveolinid foraminifers filled by equant
sparite (100–400 μm)
Partial neomorphic recrystallization of
micrite into microsparite
UM/ Umbria-Marche (Fig. 1e) Skeletal wackestone to Planktonic foraminifers (size from 10 to Sparite precipitation within the foraminifer Deep water and low-energy marine
Apennines, central mudstone 500 μm), thin-shelled bivalves, test chambers. Bioclasts recrystallization basin with pelagic fall-out deposi-
Italy/Late Cretaceous ostracodes into microsparite tion
(Cenomanian)
MO1/ Djebel Bou Dahar, microfacies A Coral-microbial boundstone Phaceloid corals (4–8 mm diameter Replacement of originally aragonite coral Coral-microbial reef at the
High Atlas Mts. (Fig. 2a) with centimetre-size corallites) encrusted by clotted skeleton by calcite microsparite; micrite margin/upper slope of high-relief
(central-eastern (1–2 cm) cement-filled peloidal micrite, intraparticle space and microsparite filling intersepta space; carbonate platform. High to mod-
Morocco)/Early Jurassic primary reef cavities filled by micrite partial neomorphic recrystallization of erate energy conditions
(Pliensbachian) Intercoralline space: peloidal-skeletal micrite into microsparite. Primary reef
packstone/grainstone with peloids cm-size cavities filled by isopachous rims
(20–400 μm), benthic foraminifers, (1–1.7 mm thick) of radiaxial fibrous
echinoderms calcite (early marine diagenesis) followed
by a drusy mosaic of blocky sparite
(0.5–5 mm equant crystal size; late burial
diagenesis). Fractures filled by equant
blocky sparite
microfacies B Laminated clotted peloidal Clotted peloidal micrite made of peloids Partial neomorphic recrystallization of
(Fig. 2b) micrite microbial (10–100 μm in diameter) embedded micrite into microsparite
boundstone (stromatolites) in micrite and microsparite forming
millimetre-thick undulose laminae
Area of peloidal skeletal grainstone with
brachiopods and peloids up to 1 mm
in size
MO2/(Djebel Bou Dahar, (Fig. 2c-d) Peloidal skeletal packstone to Peloids (50–600 μm), micrite coated Bioerosion and micrite envelops around Platform interior, shallow subtidal to
High Atlas grainstone with intraclasts (0.5–3 mm), oncoids molluscs; replacement of mollusc intertidal protected lagoon
M. Galimberti et al.

Mts.(central-eastern (0.5–5 mm), dasycladacean algae original aragonite shell by calcite equant
Table 3 (continued)

Sample/ Location/ Age Microfacies Texture (according to Components Diagenetic features Depositional environment
types (if more Dunham and Embry &
than one present) Klovan)

Morocco)/Early Jurassic millimetre-size irregular voids (Palaeodasycladus mediterraneous), sparite; equant sparite cement
(Pliensbachian) (fenestrae) benthic foraminifera (textularids, (100–800 μm) in interparticle pore space
miliolids), gastropods, bivalves and and primary voids
rare fragments of echinoderms
MO3/Djebel Bou Dahar, (Fig. 2e-f) Peloidal packstone to rarely Peloids (50–600 μm), micrite coated Bioerosion and micrite envelops around Platform interior, intertidal zone of a
High Atlas Mts. grainstone with millimetre-size ir- intraclasts (0.5–3.5 mm), benthic molluscs; replacement of mollusc original tidal flat
(central-eastern regular voids (fenestrae) foraminifera (textularids, miliolids), aragonite shell by calcite equant sparite;
Morocco)/Early Jurassic gastropods, bivalves, algae equant sparite cement (100–600 μm) in
(Pliensbachian) Thaumatoporella parvovesiculifera interparticle pore space and primary voids
Fenestrae, originated by degassing,
shrinking and organic matter degradation
in intertidal environment later filled by
both early marine (radial fibrous calcite
Effects of limestone petrography and calcite microstructure

isopachous rims) and burial equant sparite

cement
MO4/Djebel Bou Dahar, (Fig. 2g-h) Micrite coated grain and peloidal Micrite coated intraclasts (1–7 mm) Pendant and meniscus cement and meniscus Platform interior, supratidal zone of a
High Atlas packstone and grainstone from the intertidal zone, pisoids, laminated micritic crusts (vadose tidal flat
Mts.(central-eastern Areas of peloidal skeletal peloids (50–500 μm), gastropods, diagenesis); isopachous rims of fibrous
Morocco)/Early Jurassic wackestone bivalves, benthic foraminifers, algae calcite 100–200 μm thick (marine
(Pliensbachian) Thaumatoporella parvovesiculifera diagenesis); equant blocky sparite mosaic
and Cayeuxia (meteoric phreatic to burial diagenesis)
replacement of mollusc original aragonite
shell by calcite equant sparite
AS/Sierra del Cuera microfacies A Skeletal wackestone/floatstone Fragments of echinoderms, mostly Replacement of mollusc original aragonite Upper portion of a steep carbonate
(Asturias, N (Fig. 1f) crinoids (1–4 mm), fenestellid shell by calcite equant sparite slope, deposited approximately at
Spain)/Pennsylvanian bryozoans, brachiopods, bivalves, Stylolites (burial compaction and pressure 200 m paleo-water depth, border-
(Moscovian) gastropods, benthic foraminifera solution) rich in Fe and Mn oxides and a ing a shallow-water flat-topped
(Tetrataxis, Climacammina, late sparite following the reopening of the platform
Ozawainella), ostracodes, sponge stylolite
spicules in red-stained micrite matrix Intraparticle space, dissolution vugs and
rich in Fe and Mn oxides fractures filled by equant sparite cement
microfacies B Skeletal grainstone (removal of Brachiopods, fenestellid bryozoans, Diagenetic grainstone texture due to micrite
(Fig. 1g) micrite by dissolution) fragments of echinoderms (crinoids), dissolution and precipitation of equant
benthic foraminifers sparite cement (nearly 100 μm crystal
size) fills interpaticle and intraparticle
space
microfacies C Biocementstone with Radiaxal fibrous calcite embedding Radiaxial fibrous calcite cement (early
(Fig. 1h) bryozoans and brachiopods fenestellid bryozoans and marine diagenesis)
in radiaxial fibrous calcite brachiopods Cavities with late saddle dolomite cement
cement (hydrothermal late diagenesis)
 M. Galimberti et al.

Fig. 3 Comparison of the calcite

(104) XRPD peak profile of
limestone samples UM, MO2 and
MO1

and alkalis oxides, these latter far below their threshold limits. consisting of micrite matrix with sparse bioclasts (Fig. 1e),
Loss on ignition is ~44 wt% in all samples. Benchmark ideal accumulated in a deep-water pelagic depositional environ-
CaCO3 composition is CaO = 56.03 wt% and ment (Premoli Silva and Sliter 1995). The AS sample is a
CO2 = 43.97 wt%. wackestone to floatstone characterized by a red-stained
micrite matrix rich in skeletal grains and stylolites, these latter
Characterization of limestones by optical microscopy due to compaction and pressure solution during diagenesis
(Fig. 1f). Areas of skeletal grainstone and biocementstone also
The majority of the samples displays textural variability even occur: the former consists of skeletal fragments and equant
at the millimetre to centimetre scale, as shown by Figs.1 and 2. sparite in between the grains due to the removal of the micrite
A detailed petrographic analysis is reported in Table 3. matrix via dissolution processes (Fig. 1g), the latter consists of
Sample SA is a framework of sparite crystals with minor radiaxial fibrous calcite embedding bryozoans and brachio-
inclusions and lacking bioclasts (Fig. 1a–b) and can be clas- pods (Fig. 1h). The depositional environment was the upper
sified as a crystalline carbonate. SL limestone is grain- portion of a steep carbonate slope bordering a shallow-water
supported with both micrite and microsparite as matrix and flat-topped platform (Della Porta et al. 2003). The four MO
can be classified as a skeletal peloidal packstone (Fig. 1c–d). samples represent nearly time-equivalent carbonate facies ac-
Grains are mainly foraminifers, peloids and fragments of echi- cumulated adjacent to each other along a transect across a
noderms, indicative of a protected inner ramp environment Lower Jurassic carbonate platform (Della Porta et al. 2013).
(Zamagni et al. 2008). UM is a wackestone to mudstone MO1 sample is a coral-microbialite boundstone with microbi-
al encrustations, associated with peloidal skeletal packstone
Table 4 Domains size and microstrain values of calcite crystals, and grainstone areas between the corals, pointing out the tex-
determined by XRPD. Samples are listed according to increasing tural variability on the reef lithofacies even at the centimetre
microstrain values scale. Noteworthy is the occurrence of two different genera-
tions of calcite cement in the primary reef cavities (Fig. 2a):
Sample* Domains size (Å) Microstrain (10−4)
early marine isopachous prismatic crystals line the cavity wall,
SA 794(1) 0.07(1) then occluded by a mosaic of equant crystals precipitated dur-
SL 864(1) 8.48(3) ing burial diagenesis. Skeletal reef components are mainly
UM 1380(2) 5.55(2) phaceloid corals (Fig. 2b), associated with benthic foramini-
MO1 1198(2) 5.91(2) fers and fragments of echinoderms. Limestone samples MO2
MO2 737(1) 11.15(4) (Fig. 2c–d) and MO3 (Fig. 2e–f) are both mainly packstone
MO3 1188(2) 11.93(3) and locally grainstone, characterized by peloids, skeletal frag-
MO4 805(1) 12.09(4) ments and fenestrae. According to these features, the deposi-
AS 1323(2) 18.54(5) tional environment of samples MO1, MO2 and MO3 is a low-
energy platform interior, ranging from the protected subtidal
Effects of limestone petrography and calcite microstructure
Fig. 4 Relationship between age
of the limestones and calcite
crystals microstrain
lagoon to the intertidal zone. Limestone sample MO4 shows a
grain-supported and cemented texture associated with a few
millimetre wide areas of packstone. A supratidal depositional
environment is suggested by the widespread distribution of
pisoids and by pendant and meniscus cements (Fig. 2g–h).
Peloids and micrite-coated intraclasts are surrounded by three
generations of calcite: (i) on the grain surface a pendant yel-
lowish layer of fibrous cement occurs, followed by (ii)
isopachous rims of fibrous calcite and finally (iii) by equant
blocky sparite at the core of the intergranular space.
Calcite microstructural analysis by XRPD
Figure 3 shows the 28.5–30.5° 2ϑ window of the XRPD pat-
terns of the UM, MO2 and MO1 limestones, displaying the
calcite (104) reflection. The profile of this diffraction peak
varies among the samples: for UM and MO1 is well defined
and has a full width at half maximum (FWHM) of ~0.06° 2ϑ
and also the Cu-Kα2 shoulder can be observed. Conversely,
the same peak in MO2 sample is broader and has a FWHM of
~0.12° 2ϑ and the Cu-Kα2 shoulder is not anymore recogniz-
able, reflecting smaller domains size and higher microstrain
values for MO2. Furthermore, this peak exhibits nearly the
same intensity and shape in MO1 and UM, relying on very
similar microstructural features (domains size of 1380 and
1198 Å respectively). Detailed results of microstructural anal-
ysis on calcite crystals belonging to the selected limestones are
shown in Table 4; the highest domains size value is ob-
served in UM whereas the lowest one is reported for
MO2, whereas concerning the microstrain, AS and SA
represent the two end-members. Moreover, Fig. 4 points
out a correlation between the microstrain of calcite crys-
tals and the age of the limestone.
Burnability test
Table 5 reports the results of the ex situ quantitative phase
analysis on clinker_SA, _MO2 and _AS, but it is representative
of the whole set of samples. In all the samples the destabiliza-
tion of calcite and clay minerals leads to the formation of lime,
followed by the crystallization of belite and aluminates. Then,
between 1300 and 1350 °C a melt appears (inferred by the
decrease of C3A and C4AF) and also alite starts to grow.
Significant differences among the samples appear concerning
the weight percentage of the crystalline phases upon heating.
For instance at 1000 °C the CaO content is ~54 wt% and
~48 wt% in clinker_SA and _AS respectively. This difference
between these two end-members lasts up to 1200 °C. At
1450 °C all the clinkers have a composition close to the stan-
dard one, but differences among them are still observed
(Fig. 5). For instance, in clinker_AS the high content of alite
(~72 wt%) is accompanied by high amounts of belite and
ferrite (~13 and ~11 wt% respectively) whereas the amount
of C3A is limited (~4 wt%). Figure 6 highlights a correlation
 M. Galimberti et al.

Table 5 Phase composition (wt%) of clinkers samples from three size (Fig. 7b). The same at 1300 °C, by plotting C3S wt% vs
selected raw meals as obtained by Rietveld refinement, quoted for all
microstrain and domains size (Fig. 7c-d). For T > 1350 °C,
the temperatures of the burnability test
neither the microstrain nor the domains size have relevant
Temperature (°C) effects on the mixtures reactivity (Fig. 7e–f) because a
melt appears and the reactions no more take place at the
Clinker _SA 1000 1100 1200 1300 1350 1400 1450
solid state.
C3S - - - 6.3 64.1 71.2 77.7
C2S 10.3 25.0 34.3 58.8 13.2 8.4 5.3
C3A 1.3 1.0 2.7 8.1 11.8 10.5 8.7
Scanning electron microscopy
C4AF 4.4 7.3 10.4 10.1 4.3 4.8 5.9
CaO 53.6 45.8 38.4 15.5 5.5 4.3 1.7
Clinkers sintered at 1450 °C exhibit the expected phase as-
semblage, indicating the success of the thermal treatment.
Others* 30.4 20.9 14.2 1.2 1.1 0.8 0.7
High amounts of C3S and clusters of rounded and fractured
Clinker_MO2
C2S are enclosed by an interstitial matrix of aluminates
C3S - - - 32.2 59.5 69.3 69.8
(Fig. 8a); moreover, few C2S inclusions in C3S and traces of
C2S 18.4 29.2 34.4 39.7 15.9 11.7 10.1
free lime are observed. However, differences among the clin-
C3A 1.7 0.3 2.8 5.8 11.9 9.2 9.2
kers occur in terms of main phases distribution and size. For
C4AF 3.3 7.3 8.8 11.1 6.7 6.0 8.1
instance C3S appears in tabular crystals ranging from 10 to
CaO 51.6 44.0 37.0 10.8 5.3 3.1 1.9
100 μm in clinker_SA, suggesting that growth predominates
Others* 25.0 19.2 17.0 0.4 0.7 0.7 0.9
over nucleation (Fig. 8b). On the contrary, small and tabular
Clinker_AS
C3S crystals dominate in clinker_AS, revealing that the nucle-
C3S - - - 46.5 66.4 72.5 72.2
ation dominates over the crystal growth (Fig. 8c).
C2S 22.0 32.0 39.4 27.4 15.6 10.6 13.1
Furthermore, a different distribution of tricalcium aluminate
C3A 1.6 1.0 3.0 8.1 3.5 3.2 3.7
and ferrite is observed. Their overall abundance ranges around
C4AF 5.3 8.8 11.4 10.6 12.2 12.7 10.7
~15 wt% in all the clinkers as deduced by XRPD data, but in
CaO 47.7 40.9 36.3 7.2 2.0 0.9 0.3 clinker_AS C 4 AF dominates over C 3 A, vice versa in
Others* 23.4 17.3 9.9 0.2 0.3 0.1 - clinker_SA (Fig. 8c–d).
*other phases comprise C2AS, C12A7, S and CH

between the calcite microstrain and the aluminates content,
supported by high values of the coefficient of determination
of the linear regressions. Finally, Fig. 7 plots the contents of
clinker phases, as a function of the microstructural features of
the calcite crystals before the thermal treatment, at three dif-
ferent temperatures. A direct correlation between the calcite
microstrain and the C2S content at 1000 °C is found (Fig. 7a);
no correlation occurs when data are plotted vs the domains
Discussions
The limestones here investigated are similar from a mineral-
ogical and chemical point of view but have a high textural
variability both at the macro (fossil content, grain types, dia-
genetic features) and micro scale (calcite crystals microstrain
and domains size). This reflects their different depositional
environments, geological ages and diagenetic histories. Up

Fig. 6 C3A (triangles) and C4AF (circles) wt% in clinkers obtained at

Fig. 5 RQPA results (wt%) on clinkers obtained at 1450 °C, normalized 1450 °C, plotted as a function of the microstrain of the calcite crystals
to 100 wt% of crystalline phases belonging to the limestones used in the raw meal
Effects of limestone petrography and calcite microstructure
Fig. 7 RQPA results (wt%), at different temperatures, plotted as a function of microstrain and domains size. C2S at T = 1000 °C (a and b). C3S at
T = 1300 °C (c and d). C3S at T = 1400 °C (e and f)
to three microfacies are observed at the thin-section scale
in limestone AS, whereas microstrain spans significantly
as a function of the depositional environment and the
diagenetic history.
Several authors reported the influence of limestone micro-
structural features on the thermal decomposition of carbonates
and on the reactivity of the resulting products. Soltan et al.
(2011) pointed out how the fossil content and the parent cal-
cite microstructure in grainstones reflect on the reactivity of
the derived lime; furthermore, the mineralogical and chemical
composition has been proved to be the main controlling var-
iable on the reactivity of mud-supported limestones even after
calcination (Soltan et al. 2012), as also demonstrated by
Marinoni et al. (2012a) describing the role of dolomite during
calcite decomposition. At our knowledge, research projects
reporting how the limestone features affect the whole
clinkerization process, in terms of mineralogy and morpholo-
gy of the obtained clinker, still lack.
Clinker quantitative phase analyses results remark that
predicting the clinkerization relying on the overall limestone
texture is a difficult task. The effects of each single textural
feature (i.e. rock texture, grain size, dolomite content, etc) do
not sum additively, but interact among them making thus im-
possible to determine unequivocally the overall burnability.
For instance, limestones UM and SA, which are the two end
members of the Dunham’s classification, mudstone and

Fig. 8 SEM images of clinkers
sintered at 1450 °C. a clinker_
MO4 uniform phase distribution:
tabular C3S and well-rounded
C2S. C3A and C4AF occur as in-
terstitial phases. b Clinker_SA
C3S crystals up to ~100 μm and
clustered C2S close to the voids. c
clinker_AS with small C3S crys-
tals and few C2S inclusions in
C3S. d Large C3A and interstitial
C4AF between tabular C3S crys-
tals with few C2S inclusions
(clinker MO1)
crystalline carbonate respectively, lead to a final clinker with
similar mineralogy and texture. Conversely, limestone UM
and AS, both mud-supported limestones, behave differently
during clinkering. No relationships between their petrographic
features and the way the burnability proceeds can be ascertain.
Hence, the present research proposes an alternative ap-
proach to predict the raw meals burnability. It was observed
that the microstrain of calcite crystals drives the way the
clinkerization proceeds, even when calcite is fully
destabilized: the higher the microstrain, the better the
burnability of the raw meal. A limestone with high-strained
calcite leads simultaneously to larger contents of calcium sil-
icates and lower unreacted lime than the ones observed using a
low-strained calcite in the raw meal. Comparing the two end
members referring to calcite microstrain, at 1300 °C it is clear
that the higher the microstrain the higher the C3S concentra-
tion, as well as the lower the CaO amount in the final clinker at
1450 °C (clinker_SA and clinker_AS report an uncombined
lime content of ~2 and lower than 1 wt% respectively).
Therefore, it is proved that the clinker calcium silicates forma-
tion through solid state reactions is strongly influenced by the
calcite crystals microstrain, whereas the domains size has no
relevant effects. This correlation between microstrain and clin-
ker phases amounts nearly cancels out when the liquid ap-
pears. From now on, the driving factors of the clinker phases
formation are the liquid phase amount, viscosity and surface
tension.
Despite the thermal behaviour of the raw meals becomes
similar at the highest temperatures, the different early
burnability observed among the samples results in clinkers
with different mineralogy and morphology. Starting from
high-strained calcite, well-faceted small crystals of alite are
embedded in an interstitial matrix dominated by ferrite. In this
M. Galimberti et al.
case it can be presumed that primary phase volume of C3A
tends to disappear because Al3+ enters the C3S structure, thus
resulting in a decrease of Al3+ available for the C3A and caus-
ing a shift of its volume to a smaller value than the expected
one (Uda et al. 1998).
Last but not least, a relationship between the limestone age
and the calcite microstrain is found: the older the limestone,
the higher the average value of calcite microstrain (Fig. 4). In
the oldest limestones the calcite crystals were subjected to
several superimposed diagenetic processes (i.e. marine and
burial cementation, compaction, dissolution, reprecipitation
and recrystallization), in non-equilibrium conditions and in
high-straining environments. This induces defects or local
variations in the long-order periodicity of calcite crystals lat-
tice. In particular, the oldest limestones (AS and MO samples)
highlight textural features, such as fractures or several cement
generations, related to intense diagenetic processes due to the
evolution of sedimentary basins and regional geodynamic
processes developed through time. Moreover, these various
scale deformations and diagenetic phases induced stresses al-
so at the microscopic scale in the calcite crystals. It is worth
noting that a deviation from the linearity is observed for sam-
ple MO4, showing a lower microstrain than the expected one,
compared with the coeval MO1, MO2 and MO3 limestones.
This discrepancy is tracked back to the fact that the XRPD line
profile analysis provides an average value for domains size
and microstrain: sample MO4 is a Jurassic micritic limestone
crosscut by tardive veins of sparite, that experienced a shorter
diagenesis. Therefore sample MO4 microstrain value, shifting
towards a lower value compared to coeval samples, is the
result of a different diagenetic history. A similar conflict be-
tween age and microstrain is detected also dealing with sam-
ples UM and SL, where UM is older than SL but has a lower
Effects of limestone petrography and calcite microstructure
microstrain value. The discrepancy is again due to different
diagenetic histories: sample UM settled in a marine basin that
underwent a simpler diagenetic history, compared to the fold-
and-thrust belt from which sample SL is from.
Conclusions
The burnability of industrial raw meals usually employed for
OPC clinker production was investigated. All the raw meals
were similar from a chemical and mineralogical point of view,
making them comparable. Differences concerning their ther-
mal behaviour can be ascribed to the features of the carbonate
fraction.
Predicting the raw meal burnability as a function of the
limestone overall petrography represents a difficult task, be-
cause the final result is not the mere sum of the effects of each
single feature. This made necessary to look for a single pa-
rameter controlling the burnability: it was found that the
microstrain of the calcite crystals belonging to the carbonate
fraction matches this requirement. It relies on the limestone
age and it influences the raw meal early burnability in terms of
calcium-silicate phases growth and lime consumption: the
higher the microstrain, the better the burnability. Then, when
the melt appears, this correlation cancels out. However, the
different early burnability reflects in the final clinker texture:
well-faceted alite crystals immersed in an interstitial matrix
where ferrite dominates over tricalcium aluminate starting
from high-strained calcite, vice versa from low-strained
calcite.
Acknowledgements The authors are grateful to Federica Angeloni and
Alessandro Tombini from Italcementi for the support during the
burnability tests and for the XRF analyses. Constructive reviews by
Dario T. Beruto and by an anonymous expert and the journal editor
Dogan Paktunc are gratefully acknowledged.
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