Provenancing of cement using elemental analyses
and isotope techniques –the state-of-the-art and
future perspectives
Anera Kazlagi´
c, *
a
Jochen Vogl,
a
Gregor J. G. Gluth
b
and Dietmar Stephan
c
With the aim of identifying the origin and the manufacturer of a cement, a reliable procedure that provides
unambiguous results is needed. Such procedure could resolve practical issues in damage research, liability
issues and forensic investigations. A substantial number of attempts for fingerprinting of building materials,
including cement, has already been carried out during the last decades. Most of them were based on
concentration analysis of the main elements/components. This review provides an overview of
provenance studies of cement and the main approaches commonly used. Provenance studies of cement
via isotope techniques are also presented and discussed as representatives of the state-of-the-art in the
field. Due to the characteristic properties and the occurrence of carefully selected isotope ratios, unique
fingerprints of different kinds of materials can be provided by these methods. This property has largely
been explored in various scientificfields such as geo- and cosmochemistry, food forensics, archaeology,
geochronology, biomedical studies, and climate change processes. However, the potential of isotope
techniques in cement and concrete research for provenance studies has barely been investigated.
Therefore, the review outlines a suitable approach using isotope ratios, which could lead to reliable
provenancing of cementitious materials in the future.
Anera Kazlagi´
c obtained
a master's degree in chemistry
(2018) from Faculty of Science,
University of Sarajevo (UNSA).
Anera received two silver badges
from UNSA, for being one of the
best students of 1
st
and 2
nd
study
cycle. Aer graduation, she was
employed at UNSA as teaching
and research assistant. Since
December 2019 she is working
as a scientic researcher at the
division Inorganic Trace Anal-
ysis, Bundesanstalt f¨
ur Materialforschung und -pr¨
ufung (BAM),
Berlin, Germany. Anera is enrolled as PhD candidate at Depart-
ment of Civil Engineering, Building Materials and Construction
Chemistry at Technische Universit¨
at Berlin. Her current research
interests concern isotope research in cement, with the focus on
provenancing.
Dr Jochen Vogl studied chemistry
at the Universities of Regensburg
and Mainz in Germany with
a focus on speciation analysis
with on-line IDMS in his doctoral
thesis (1997). He then worked for
two years on reference measure-
ments applying IDMS at the
IRMM (now JRC Geel) in Bel-
gium. Since January 2000 he is in
charge of the eld Isotope Anal-
ysis at the Bundesanstalt f¨
ur
Materialforschung und -pr¨
ufung
(BAM) in Berlin, Germany. His main working elds are the appli-
cation of IDMS for reference measurements, isotope ratio analysis,
isotope and matrix reference materials, elemental mass spectrom-
etry in general and metrology in chemistry.
a
Federal Institute for Materials Research and Testing, Division 1.1 Inorganic Trace
Analysis, Richard-Willst¨
ater-Straße 11, 12489 Berlin, Germany. E-mail: anera.
b
Federal Institute for Materials Research and Testing, Division 7.4 Technology of
Construction Materials, Unter den Eichen 87, 12205 Berlin, Germany
c
Technische Universit¨
at Berlin, Department of Civil Engineering, Building Materials
and Construction Chemistry, Gustav-Meyer-Allee 25, 13355 Berlin, Germany
Cite this: J. Anal. At. Spectrom.,2021,
36,2030
Received 28th April 2021
Accepted 2nd September 2021
DOI: 10.1039/d1ja00144b
rsc.li/jaas
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JAAS
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Introduction
The built environment is one of the most signicant achieve-
ments of human civilisation, because with buildings it provides
protection against environmental inuences and the basis for
the production of goods, but with transport systems, it also
provides the basis for all forms of traffic. Concrete is the basis
for this in most cases, which is why concrete has become the
material that is articially produced in the largest quantity by
human hands during the last hundred years. The concrete
properties are dominated by the reactive component cement,
which is the synthetic chemical product produced in the largest
quantity. Due to the ageing of concrete as a building material
due to environmental inuences, but also due to application
errors caused by faulty constructions or wrong mix composi-
tions of concrete, various structural damages occur worldwide,
which cause high costs and, in severe cases, even endanger
human lives. Aer their occurrence, damages are being
preventively investigated and researched. Intending to mini-
mise the consequences of damages, it is crucial to identify the
source and the cause that lead to such events. Therefore, one of
the main reasons for cement provenancing is identifying the
causes of failure in concrete structures. Poor and substandard
building material, primarily steel reinforcement, structural
steel, and cement represent the main causes of building failure
and collapse.
1
Concrete roof collapses are occurring worldwide.
2
According to a recent review by Proske and Schmid,
3
the annual
collapse frequency of buildings is 2.4 10
7
per year in
industrialised countries, and 4.7 10
6
per year in developing
countries, in many cases caused by insufficient quality of the
employed building materials. The authors also determined
mortality rate values of building collapses, ranging from 9.8
10
8
to 1.5 10
6
per year, for industrialised and developing
countries, respectively, which is in agreement with the value
obtained by Blockley.
4
Furthermore, bridge collapse frequencies
worldwide have been reported to be on the order of magnitude
of 10
4
per year.
5
Many government agencies tried to develop a protocol and
a guideline to reduce and prevent the risk of such catastro-
phes. The type and origin of the construction and raw mate-
rials used, and the manufacturer of the components are of
great relevance not only for avoidance and damage assessment
but also for the resulting liability issues. This is also of interest
when considering the stability of concrete,
6,7
marble,
8,9
and
stone
10–15
in historic structures and investigating the origin of
the raw materials from which those structures were made. For
example, previous studies emphasized the investigation of raw
materials from which buildings in Portugal were con-
structed.
16
In most structural failure cases, analysis of the
building materials, including cement as the major compo-
nent, is one of the key issues for understanding the quality and
the strength of the structure. Testing institutes are also
interested in provenance studies, since they are sometimes
asked whether two cementitious samples are identical or are
ofthesameorigin.
17
Recycling of rubble may also require provenance studies in
some cases. Furthermore, the determination of rubble prove-
nance can contribute to expand the knowledge about this
material, and also about possible ways to return the material to
the construction processes.
Beyond this, cement provenancing is required in forensic
investigations. Given the variety of possible circumstances
that may be encountered on the crime scene, any building
material, such as cement, mortar, or concrete, may hold
evidentiary signicance. This includes cement particles or
dust found at a crime scene. Those particles can serve as
a physical evidence linking a suspect(s) to the victim or the
crime scene. Knowing the origin of the cement and concrete
Dr Gregor J. G. Gluth is a senior
researcher at the Bundesanstalt
f¨
ur Materialforschung und
-pr¨
ufung (BAM), Berlin, since
2010. Previously he had worked
at the institute for civil engi-
neering of the Technische Uni-
versit¨
at Berlin, where he also
obtained his PhD. He is active
member of several committees of
the International Union of
Laboratories and Experts in
Construction Materials, Systems
and Structures (RILEM) and the European Federation of Corrosion
(EFC). His research is focussed on concrete degradation mecha-
nisms, durability, and maintenance as well as special cements and
cements with reduced carbon footprint.
Prof. Dr Stephan Dietmar
studied chemistry at the
University of Siegen in Germany
with a focus on building chem-
istry (1996). He then worked for
three years as a research assis-
tant at the Institute for Building
Materials and Construction
Chemicals (University of Sie-
gen). Aer that, he was
employed as a trainee and
senior scientist at “Cement &
Quality, Heidelberg Cement”in
Heidelberg, Germany. For one year he worked at Heidelberger
Cement Group Technology Centre GmbH as a senior scientist. In
the period 2001–2006 he was working as a postdoc at TU Munich,
and aer that as academic senior councillor at the Department of
Construction Materials and Building Chemistry at University of
Kassel, Germany. Since March 2011 he is working as professor for
Building Materials and Construction Chemistry at TU Berlin.
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particles can be benecial for locating the crime scene,
tracking back the particles to a packaging unit or providing
furtherevidenceforuseincourt.
Geographical provenancing of any kind of material can be
described as an act of identifying the place of origin or the
source of the material. Knowing the geographical origin of
a specic material has been very useful in elds such as
forensics and archaeology for unravelling residence histories of
suspects or trading routes between past cultures. The basis of
provenance studies is that there are specic, recurrent and
denable interdependences between raw materials and the
nal products derived from them.
18
Therefore, we can summarise three main cases:
(1) Finished product correlates to a raw material used in the
production, e.g. marble.
(2) Processed material, within which one component domi-
nates, either in terms of the mass fraction or in other terms, e.g.
curse tablets made of pure lead.
(3) Complex mixtures or a highly processed material, e.g.,
alloys, cement.
The provenancing of any material can be determined by
utilising specic properties of the material under investigation
and it's preceding (original) raw material.
Cementsforgeneralpurposesaredened in the standard
EN 197-1:2011,
19
which differentiates between ve main cate-
gories: CEM I Portland cement, CEM II Portland-composite
cement, CEM III Blast furnace cement, CEM IV Pozzolanic
cement, CEM V Composite cement. Portland cement clinker,
the main component of ordinary Portland cement (OPC; CEM
I according to EN 197-1:2011), is produced by sintering a nely
ground raw meal consisting mainly of limestone and clay or
the natural mixture marl from local materials. Other natural
raw materials, such as quartz sand, or secondary raw mate-
rials, such as foundry sands, slags, etc., can also be used to
adjust the composition. In the rotary kiln, the mixture is
heated to a temperature of approximately 1450 C. In addition
to hard coal and lignite, a complex mix of different secondary
fuels is usually used in clinker production to achieve high
temperatures. The OPC clinker is mixed with a certain amount
of different calcium sulphate minerals and then nely ground
to give OPC. The calcium-rich components of OPC that do not
originate from local sources are primarily the calcium
sulphates which either come from industrial by-products such
as gypsum from ue gas desulphurisation plants (FGD
gypsum
20
) or partly from natural sources such as natural
anhydrite and gypsum. Cements other than OPC contain
additional constituents, suchaslimestonepowder,ground
granulated blast furnace slag, natural pozzolana, yashor
burnt oil shale. Due to this broad range of components with
different geographic origin, the provenancing of cement is not
straightforward.
This paper provides an overview of published provenance
studies of cement and concrete and lists the main approaches
usually adopted. Provenance studies of cement utilising isotope
techniques are also presented and discussed as representatives
of the state-of-the-art in the eld.
Previous attempts for cement
provenancing
Elemental ngerprinting
Trace elements analysis is being performed in different scien-
ticelds and for provenance studies of various inorganic
materials. Trace elemental pattern was used for establishing the
provenance of pottery,
21
archaeological mortars,
22,23
as well as
for clinker and cement, which is described in this section.
For element to be used in cement provenance analysis, the
local raw materials must be the predominant source. It should
not originate from the ancillary components, the used fuel, or
the furnace. Furthermore, its concentration must be indepen-
dent of the temperature uctuations in the kiln. For the concept
to be transferred from cement to concrete, the elements must
be highly immobilised in the alkaline pore solution.
24
While
reviewing the literature, we noticed that many authors investi-
gated major, minor and trace elements in the studies. However,
trace element label in these studies partially differ from the
denition put forward by IUPAC.
25
Therein, trace element is
considered as any element having an average mass fraction of
less than about 100 mgg
1
.
The rst paper on the provenancing of cement was pub-
lished in 1993 by Goguel and St John in two parts. In the rst
part,
24
major, minor and trace elements present in New Zealand
cements were investigated by semiquantitative Inductively
Coupled Plasma Mass Spectrometry (ICP-MS) and quantitative
Atomic Absorption (AA), Atomic Emission (AE) and Inductively
Coupled Plasma Optical Emission Spectrometry (ICP-OES).
Cement samples were prepared by digestion in a mixture of
HF and HClO
4
, followed by dissolution in diluted HNO
3
. The
authors concluded that Ca/Sr, Ca/Ba and Ca/Mn ratios have the
greatest potential for identifying cements in hardened
concretes and that the Ca/Sr ratio seems to be the most accu-
rately quantiable measurand. The variation of the Ca/Sr ratio
of cement from the same production site over a long period is
small, making this ratio suitable for discriminating between
production sites. Rare earth elements (REE) distribution
pattern, which were analysed as well, showed more limited
identication potential. In the second part,
26
the authors dis-
cussed Ca, Sr and Mn concentration leached from the concrete.
By performing selective acid cement leaching from hardened
New Zealand concretes, authors have tried to determine its
source of manufacture. Crushing the concrete and selecting the
fragments allowed them to exclude coarse aggregate from
leaching, while a small portion of ne aggregates could not be
excluded. The authors tested four types of aggregates to deter-
mine their contribution to leachates from concrete. It was
concluded that it is essential to assess the contributions from
the aggregates to the leaching solution. The application of REE
distribution pattern to provenance the cement in a hardened
concrete is limited by contamination of REEs released from
aggregates during leaching. These two articles triggered further
research in this eld. Tamas and co-authors noted that
cement's origin determination is both scientically and practi-
cally a challenge which could be solved by analytical
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determination of certain elements contained in cements, and
statistical processing of analytical data. In their study they
stated that a three-element approach based on Sr–Ba–Mn is not
fully adequate, especially in case of sulphate resistant clinkers
having high iron content.
27
Therefore, they added Mg, Ti and Zr, nally ending up with
a six-element approach, realised by ICP-OES measurements and
statistical processing of the data, using “pattern recognition”
methods.
28
In another project, Tamas and co-authors analysed minor
and trace elements in een clinker sorts to classify the clinkers
produced in different factories in Spain. For the qualitative
identication of clinkers a rule base classier was designed -
trained by C4.5 algorithm.
29
In 2001 and 2002, Tamas and
Abonyi investigated the content of minor and trace elements in
OPC clinkers, and their use for provenancing. They determined
the Mg, Sr, Ba, Mn, Ti, Zr, Zn and V content in several hundred
clinkers. The maximum and minimum values, the standard
deviation of data, as well as the real and rounded averages were
used for plotting (Table 1). The authors concluded that the rst
six elements come from the local raw materials, while Zn and V
mainly come from fuel and are not useful for provenance
determination. They considered Ba, Sr and Mg as the most
relevant elements for clinker ngerprinting.
29
The sample
preparation was made by dissolving the clinker in HCl, followed
by SiO
2
precipitation, ltration and washing steps. The ltrate
was analysed by ICP-OES, statistically processed via MATLAB©
and the “star plots”were constructed (Fig. 1). Star plots are
a graphical method used to simplify and to visualize the minor
and trace element content in clinker, by comparing it with the
proposed standard. The area of the star in a star plot is
proportional to the total amount of the considered elements,
and the eight rays of the star represent the eight elements.
However, among other elements, Zn and V were still used for
constructing “star plots”. The trace elements were selected
based on the obtained clusters by the modied version of the
Fisher interclass separability method. For clinker identication
a specicsoware was developed
30
which is available on
internet.
31
The soware relies on unsupervised fuzzy clustering,
identied by a fuzzy classier using a control algorithm.
32
In 2004, Abonyi and co-authors presented a paper in which
data presentation box and quantile–quantile plots were
proposed to analyse the relationships between different facto-
ries and different minor and trace elements in clinkers.
33
The
authors concluded that exploratory data analysis can be useful
in the qualitative analysis of elemental content in clinker.
According to Lin and co-authors,
34
a standard pattern of each
origin must be established prior to the identication of the
clinker origin. Since each clinker origin shows a broad range of
trace element patterns, the uncertainty resulting from dening
a distinctive compound pattern from its various forms makes
these techniques difficult for usage. Therefore, it is not easy to
dene a precise standard pattern of a clinker origin. Commonly
applied mathematical models for solving these uncertainty
issues are the random model, the fuzzy model
35
and the Gray
model.
Proposed by Deng in 1989, the Gray relational analysis is
a geometric method that can measure the approachability or
similarity between series.
36
Lin and co-authors' study integrated
Table 1 Maximum and minimum values, standard deviation, averages, and rounded averages (used for star plots) of investigated clinkers
(mg kg
1
) reprinted from F. D. Tamas and J. Abonyi, Cem. Concr. Res., 2002, 32, 1319–1323, Copyright (2002), with permission from Elsevier
Element Maximum value Minimum value Standard deviation Average Rounded average
Ba 442 47 122.74 192.68 200
Mn 6538 15 995.06 507.02 500
Sr 2972 19 677.63 560.28 500
Ti 1691 175 289.78 1189.13 1000
Zr 149 4 17.33 47.32 50
Mg 24 125 1751 6453.27 8976.93 8950
Zn 559 11 112.89 113.7 100
V 297 17 67.11 85.69 100
Fig. 1 Star plot of a Hungarian clinker (code number 5L5), a Spanish
one (code number 89ES1) and a South African one (code number
159SA17). Reprinted from F. D. Tamas and J. Abonyi, Cem. Concr. Res.,
2002, 32, 1319–1323, Copyright (2002), with permission from Elsevier.
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both concepts of Gray number and Gray relational analysis to
set up a model for qualitative identication of clinker. The
results showed that proposed model was successful in identi-
fying the origin of clinker. The authors concluded that the
methodology of the model can be extended to various areas with
similar uncertain information.
In his doctoral thesis entitled “Chemical identication of
Portland cements produced in Poland on the basis of the
content of trace elements”, D. Kalarus determined Cr, Zn, Cd,
Pb, Co, Ni, Co, Sr, Ba, Mn, Ti and Mg. The analytical method
which the author used for the research was ICP-OES and scan-
ning electron microscope (SEM). Based on the concentrations of
the elements in clinkers, cements and raw materials, it was
concluded that Mg, Sr and Mn serve as “markers”for the
chemical identication of CEM I produced in Poland.
37
The
author concluded that the concentration of these elements in
cement depends almost exclusively on their content in the raw
materials, and not on the substitute fuels or waste materials
such as used car tires and municipal waste, which is in agree-
ment with the statement by Tamas and Abonyi. Other studies
on cement and clinker provenancing were mostly presented as
a conference proceedings or conference papers.
38–41
Sawaki and
co-authors estimated the chemical composition of cement in
hardened concrete via an electron probe microanalyser, but the
sensitivity turned out to be insufficient for discrimination.
42
Kasamatsu and co-authors
43
examined elemental (Cu, Rb, Zn,
Sr, Zr, Ba, La, Ce, Nd and Pb) discrimination in nitric acid
soluble components of concrete. According to the authors, this
method can be used for forensic discrimination. However,
Goguel and co-authors
26
concluded that the nitric acid leaching
approach is not applicable to aggregates consisting substan-
tially of limestone. Therefore, nitric acid soluble component of
concrete cannot represent a cement sample, but rather a mix of
cement and calcareous additives. Moreover, dissolving concrete
in nitric acid results in signicant extraction of the lanthanides
from aggregates, which removes the potential of lanthanides for
cement identication in concrete.
26
In several papers, MATLAB© and the star plot method were
used to potentially pinpoint the origin of cement and, in some
cases, mortars.
44–46
A summary of the previous attempts for
clinker, cement and concrete provenancing is shown in Table 2,
where “elemental ngerprint”includes algorithm, pattern
recognition and geometric methods, considering that for its
realisation and interpretation, elemental analysis is a prerequi-
site. “Isotope ratio”implies the application of one isotopic ratio,
e.g.
87
Sr/
86
Sr. In summary, the elemental ngerprint approach
requires a large number of samples and the selection of appro-
priate (major, minor and trace) elements for establishing a stan-
dard pattern of clinker and later cement. Most of the previous
research relied on multivariate statistical analysis. Such methods
cannot be used for evaluation of all elements. This is because
these elements either have no relation to the geographic origin or
they are related to additives, whose origin is not connected to the
origin of the major components, such as fuel used in production
(used tires, heavy fuel oil etc.). Besides that, to have a meaningful
result, many samples and parameters should be considered.
Sufficiently large numbers of the target elements and as well of
the samples are needed to achieve statistical signicance; other-
wise, the results are meaningless due to high standard errors. In
several studies, these requirements were met and the origin of
clinker for certain locations was determined via different
approaches. Clinker is an intermediate product, which is avail-
able only at the production site and therefore, the practical rele-
vance is rather limited. The identication of clinker in cement
and hardened concrete, however, remains an open question.
Table 2 Summary of previous attempts for clinker, cement and concrete provenancing, “elemental fingerprint”includes algorithm, pattern
recognition and geometric methods, considering that for its realisation and interpretation, elemental analysis is a prerequisite. “Isotope ratio”
implies application of one isotopic ratio
Clinker Cement Concrete Elemental ngerprint Isotope ratio Year Reference
x x 1993 24
x x x 1994 26
x x 1996 27
x x 1997 28
x x 1997 38
x 1998 39
x x x x 2000 48
x x 2001 29
x x 2002 30
x x 2002 35
x x 2003 44
x x 2003 45
x x 2003 40
x x 2004 33
x 2005 17
x x 2007 49
x x 2007 46
x x x 2007 37
x x 2008 34
x x 2018 43
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Isotope studies
One of the most suitable techniques which can be used in the
provenancing of building material is isotope ratio analysis of
metal elements by means of mass spectrometry. The basic
principle of all mass spectrometers is ionisation of a sample in
an ion source, separation of the ions via a mass separator
according to their m/z(mass/charge) ratio and nally, their
detection at a detection unit.
47
Thermal Ionisation Mass Spectrometry (TIMS) and Induc-
tively Coupled Plasma Mass Spectrometry (ICP-MS) are aer
Isotope-ratio mass spectrometry (IRMS), the most used tech-
niques for authentication purposes.
Besides TIMS, both single-collector (SC) ICP-MS
50–53
and MC-
ICP-MS
51,54
have been widely used for measuring isotope ratios.
Due to the high measurement precision, the large natural
isotope variation and the comparatively high contents in
different sample types, strontium isotope ratios have found
wide application outside of geochemistry and have been
successfully used to determine the origin of inorganic mate-
rials, archaeological artefacts
55–57
and glass.
58,59
Therefore, Sr
isotope ratios can have high signicance in cement prove-
nancing. Since the main raw material for cement production is
limestone, and plenty of limestone deposits in Europe originate
from geological formations containing calcite or dolomite, the
different geological age of limestones and the original mineral
composition combined with geological history are reected in
87
Sr/
86
Sr isotope ratio of cement.
87
Rb decays to
87
Sr with a half-
life of 4.8 10
10
years, while emitting a beta
particle.
60
Depending on the age, and the initial Rb/Sr ratio, different
geochemical reservoirs and rocks therein developed a large
variation in today's
87
Sr/
86
Sr ratios, ranging from approximately
0.702 for the depleted mantle to >0.943 for old continental
crust.
61
For the light element isotope systems, such as S, H, N, O and
C, the mass-dependent effects are signicant. Since their
isotope composition can be changed in individual process steps
(e.g. burning, annealing) by isotope fractionation, they have
limited suitability for determining the origin of cement and
concrete. Contrastingly, for the heavy element isotope systems,
such as Sr, Nd and Pb, the mass dependent effects are mostly
within the noise of the measurement and surely much smaller
than the regional natural variations that are observed in prov-
enancing applications, therefore, scientists can get a unique
insight into the material's geographic source and/or production
history.
47,62
For the elements like Sr, which have more than one
non-radiogenic isotope, the relative abundance of the radio-
genic isotope (
87
Sr expressed as
87
Sr/
86
Sr) can be normalised to
the xed nominal abundance ratio of a pair of stable isotopes of
that element (
86
Sr/
88
Sr ¼0.1194 (ref. 63)). Therefore, for Sr, only
the radiogenic portion of a certain isotope is considered, and
this special internal calibration corrects for any stable isotope
fractionation (for example, burning) independently whether it
occurs in the mass spectrometer, during sample preparation or
even before in the history of the sample.
The rst idea for using Sr isotopes as tracer for the
geographic origin of cements dates to the year 2000 when
Graham and co-authors have published a case study from New
Zealand. They combined chemical and strontium isotopic
analysis, and showed that New Zealand cements carry
geochemical ngerprints from their raw materials to the nal
product, the concrete.
48
The authors demonstrated that there
are measurable differences in the
87
Sr/
86
Sr values of most of the
cements analysed, which can be used to pinpoint the
geographic origin. The number of cement plants, however, is
rather low in New Zealand and neighbouring countries play no
role in this context. Additionally, the investigated cement and
concrete samples date back to the 1980s and earlier, which
might not be comparable to modern cement.
Kosednar-Legenstein, in her PhD thesis,
49
and in studies
with co-authors
64,65
investigated the mineralogical, chemical
and isotopic composition of historic mortars and plasters (with
burnt lime as binder) from Austria. Among other results, the
authors reported
87
Sr/
86
Sr ratios of the mortars and plasters to
be between 0.7091 and 0.7115, whereas Sr/Ca ratios did not
exceed 0.003. In addition, burning and setting experiments
were conducted to investigate the behaviour of REE and the Sr
isotopes. The authors concluded that burning has a negligible
inuence on Sr/Ca,
87
Sr/
86
Sr and REE distribution, and that
Sr/Ca and
87
Sr/
86
Sr signatures can thus, in principle, be used to
identify natural deposits used for manufacturing of the mate-
rials. However, variations of the
87
Sr/
86
Sr ratios in some of the
investigated deposits as well as the possibility that limestone
from different deposits was used for the binder and the aggre-
gates, respectively, made unequivocal provenancing difficult.
All other publications that link isotope analysis and cement
research were focused on isotope applications other than
geographical origin determination. A study performed by
Pierkes and co-authors investigated the inuence of cement
hydration on the distribution of oxygen and hydrogen
isotopes.
66
Another example is the application of stable isotopes
(elements H, C, N, O, S) to investigate reactions during curing or
concrete damage.
67–70
Recently, Grengg and co-authors investi-
gated the deterioration mechanism of alkali-activated cements
in sulfuric acid, using oxygen-isotope signatures, among other
methods and tools.
71
However, if we take a look at the other examples of inorganic
material's provenancing, we would surely notice that isotope
techniques were frequently used, mostly for studying different
categories of archaeological materials
72,73
and ceramics prove-
nancing.
74–76
In ceramics provenancing, with the aim of
assigning a production location to a specic ceramic artefact of
unknown origin, the rst step is the characterisation, followed
by identication of their chemical, physical or structural
“ngerprint”, and the last step is comparison. This comparison
is made by using collected ngerprints and advanced statistical
techniques to search for similarities and differences. This
procedure allows the collection of all ceramics with similar
features and differentiating groups of ceramics with different
properties.
77
In archaeology, lead isotopes have been used as
tracers for provenancing of metal samples and artefacts since
its introduction by Brill and Wampler in 1967.
78–80
By combining
the isotopic information with additional information on the
sources and the artefacts being independent of the isotope data,
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it is possible to overcome limitations such as overlapping lead
isotopic compositions of ore deposits, large spreads within one
ore deposit or a missing overlap with (un)known mining
locations.
57,81
A promising approach for cement provenancing is the
application of isotope ratios as described above for archaeo-
logical and ceramics provenance studies. In principle, the
transfer of these approaches to cement is possible, but works
best for approaches which have been established for glass and
ceramics due to the similarity of the materials.
The advantage of isotopic over elemental ngerprinting
Provenancing of building materials through isotope techniques
are based on the principle that every material, with a different
geographical origin, has its unique isotopic ngerprint. The
major advantage of isotope techniques is that some isotope
systems which contain radiogenic isotope, such as
87
Sr/
86
Sr, can
be linked to the geographic origin, as they reect the mineral
composition and geological history of the raw material. More-
over, radiogenic isotope systems do not change, while the
elemental concentration are exposed to changes in environ-
ment as well as in technical processes. If strontium is consid-
ered as an element of interest in cement, the isotope ratio
depends on its origin from each of these raw materials,
predominantly in limestone or marl. The current literature
reveals that various methods can be employed for the prove-
nancing of cements and clinkers. Of particular interest is the
tendency of using elemental concentrations towards less
unequivocal data, and consequently, the need for a higher
number of features (appropriate elements) in the elemental
ngerprint. Elemental ngerprints seem easier to determine
but would, subsequently, require knowledge in multivariant
statistics and data analysis to be interpreted. However, isotope
ratio determination allows simpler isotopic ngerprints, which
are unique and unambiguous. Finally, isotope ngerprinting
approach offers reduced number of measurands, leading to
a more straight forward statistical evaluation and interpretation
of data.
Other techniques
In addition to the above-mentioned analytical techniques, X-ray
diffraction (XRD) and X-ray uorescence (XRF) spectrometry are
important techniques for provenance studies. Their usefulness
was proven in various elds, e.g. the analysis of dust from
a shipment of contraband ivory to determine the original
location where the ivory was packed,
82
or solving a double
murder case in Australia,
83
where X-ray diffraction allowed to
identify soils on a tool and from a quarry, but also for solving
other forensic cases.
84
In principle, this capacity could be also
used for provenancing of concrete particles found on a crime
scene, and their possible agreement with samples from a sus-
pected quarry. For example, quartz gravels and sands, used as
aggregate for concrete, differ as regards crystallinity,
85
which
can possibly be exploited for provenance studies. Besides XRD,
XRF was very oen used for characterising and provenancing of
different types of building materials,
86,87
predominantly old
stones
8,15,88
and marbles
9,89
in buildings or artifacts with
historical signicance. Both XRD and XRF were used for
establishing the provenance of limestone.
90
With the purpose of
collecting both XRD and XRF data on the same spot of an object,
a portable XRD/XRF
91
instrument was developed. Another
technique which was used for limestone,
92,93
but also for
pottery
94–96
provenancing was Instrumental Neutron Activation
Analysis (INAA). Meyers and Vanzelts used INAA in their pilot-
study
97
to distinguish between objects made of limestone from
different sources.
Another technique worth mentioning is laser ablation (LA)
ICP-MS. Van Ham-Meert and co-authors
124
published an article
about LA-ICP-MS for Pb and Sr isotopic determination in
archaeological glass. This technique was also used for prove-
nancing of ceramics,
98,99
as well as for cultural heritage
research.
100,101
The study of using portable LA for sampling solid
materials, with subsequent Sr and Nd measurements on TIMS
was reported by Knaf and co-authors.
102
An additional promising method for isotopic microanalysis
is laser ablation molecular isotopic spectrometry
103
(LAMIS). In
their article,
104
Bol'shakov and co-authors evaluated LAMIS for
rapid optical analysis of isotopes of different elements. Appli-
cation of LAMIS for optical isotopic analysis of solid samples
was also investigated in a paper published by Mao and co-
authors,
105
where measurement of strontium isotopes showed
promising results. In forensic analysis, for an unknown soil
sample, scanning electron microscopy with energy dispersive X-
ray spectrometry (SEM-EDX) allows recognition of the presence
or absence of man-made particles, including concrete and
cement.
106
Therefore, automated mineralogy is amenable to
distinguish and recognise the particles derived from common
construction material classes. Indubitably, all these techniques
can provide valuable information for elemental and phase
identication and quantication in cement, which can be very
benecial for an overall picture in provenance study.
Since cement and concrete are both highly processed mate-
rials, IRMS is not covered within this review, since it relies on
analysis of light element isotope systems whose composition
can be strongly changed by isotope fractionation, as explained
in the section “Isotope studies”and thus tracing back cement to
the source materials is impossible.
The combined approach for
provenancing
The combined approach for provenancing, as proposed here,
incorporates the use of
87
Sr/
86
Sr and
143
Nd/
144
Nd isotope ratios
and of Ca/Sr elemental ratios to provide a unique ngerprint of
cement. The whole pathway for cement provenancing is shown
in Fig. 2.
Structure of the combined approach
First, a sample should be subsampled for mass fraction deter-
mination and isotope ratio analysis. For isotope ratio analysis,
a selection of the sample preparation procedure is very
important.
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For trace elements like Sr and Nd, prior to isotope ratio
analysis, mass fraction determination should take place pref-
erably on ICP-MS or ICP-OES. The following step is matrix
separation, to purify the small quantity of analytes. To obtain
accurate and precise isotope ratios, it is recommended to
perform the
87
Sr/
86
Sr and
143
Nd/
144
Nd measurements by TIMS,
on a single and on a double or triple lament geometry,
respectively. When both Sr and Nd isotopic ngerprints are not
capable of completely resolving the different cement origins,
a third parameter should be introduced. Here, Ca/Sr concen-
tration ratio could be a promising measurand which could help
distinguishing between samples with very similar
87
Sr/
86
Sr–
143
Nd/
144
Nd isotopic ngerprint. This parameter is
promising and has already been studied by Goguel and co-
authors.
26
To measure total concentration, an element must be
fully dissolved. For this purposes, total digestion in HF and
HNO
3
are oen used. Due to the many reasons, such as pres-
ence of calcium as a major constituent in cement and the
formation of CaF
2
precipitate while dissolving cement in HF
and HNO
3
, numerous interferences on ICP-MS, as well as time-
consuming sample preparation, these measurements are rec-
ommended to be carried out using X-Ray Fluorescence (XRF) on
cement glass beads. Once prepared and properly stored, fused
(glass) beads are very stable and can be used several times.
Improvement by adding another isotope system
In the past mostly one isotope system (isotope ratios of one
chemical element) has been used for provenancing. For
complex materials such as alloys or glass, which consist of
several components of different geographical origin, one
isotope system, however, oen resulted in large overlaps and
insufficient resolution of the measurement space. To solve this,
additional isotope systems were introduced for glass prove-
nancing.
58,59,107,108
In 2009, Henderson and co-authors published
a paper on the provenancing of glass in the Islamic Middle East
by using oxygen, strontium, and neodymium isotope systems.
They concluded that the determination of Nd and Sr isotope
ratios for selected samples would be a suitable approach for
providing independent geographical information.
58
Elements such as Sr and Nd display variations in their
isotopic composition since one or more of their isotopes is the
nal product of the decay of naturally occurring and long-lived
radionuclides. Consequently, the isotopic composition of such
radiogenic isotopes is governed by the initial parent/daughter
ratio and the time these nuclides have spent together.
Therefore, the isotopic composition of these elements is not
only used for geochronological dating purposes but also for
tracing the geographical origin.
Neodymium is a classical isotope tracer in geochemistry and
has been used widely for dating and the study of petrogenesis,
alteration, and weathering processes.
109–111
Due to its affinity to
silicate phases, the Nd isotope system has been applied in
addition to the Sr isotope system in provenance studies of
glass.
59,108,112–116
147
Sm decays to
143
Nd while emitting an alpha
particle with a half-life of 1.06 10
11
years.
117
Besides using this
decay system for dating purposes, it can be used as a natural
tracer since the isotopic composition of Nd as measured today is
time-integrated results of Sm/Nd ratio in a specicenviron-
ment.
118
The assumption is that
143
Nd/
144
Nd ratios are different
in the raw materials from different (geographically located)
plants used for clinker, and therefore also for cement production.
Sr is the tracer for the calcium carbonate-bearing raw material
(limestone or marl), and Nd for the silicate-bearing raw material
(clay). The addition of neodymium isotopes as a second param-
eter offers the potential to achieve results that provide more
information about the geographical origin and empower the new
approach for provenancing. This is already demonstrated by
Henderson and co-authors, who applied both Sr and Nd isotope
ratios for glass provenance studies. When it comes to cement
a similar approach might be feasible, because cement and glass
have much in common. Both materials are complex mixtures of
a silicate and a carbonate component and contain a suite of
minor additives. Aer mixing, both materials are exposed to
temperatures above 1400 C hampering the application of clas-
sical stable isotopes of elements such as H, C and O. In Fig. 3 the
87
Sr/
86
Sr and
143
Nd/
144
Nd isotope measurements in Bronze Age
glass are plotted versus each other. This diagram clearly shows
that Mesopotamian glasses can be differentiated from Egyptian
Fig. 2 The pathway for cement provenancing.
Fig. 3 A plot of
87
Sr/
86
Sr vs.
143
Nd/
144
Nd isotope measurements in
Bronze Age glass from Mesopotamia (lozenges), Egypt (squares) and
Greece (triangles). Adapted from Henderson and co-authors, 2010.
107
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and Greek glasses based on their combined
87
Sr/
86
Sr and
143
Nd/
144
Nd signatures, which is not possible based on the
87
Sr/
86
Sr signatures or the
143
Nd/
144
Nd signatures alone.
107
Samples which cannot be resolved by using one isotope system,
because the data overlap within the measurement uncertainty,
might be resolved by a second isotope system, adding a third or
fourth measurand, whether it is an isotope ratio, an interelement
ratio or an element concentration, will even increase the resolu-
tion, provided the measurand is correlated with the origin of one
of the raw material.
General limitations
The selection of a sample preparation procedure has an
important role in cement provenancing. If we consider prove-
nancing of CEM I, the total analyte's content and isotopic
ngerprint in minor additional constituent must be assessed.
Gypsum present in cement is exclusively from non-local sour-
ces, and Ca bearing minerals always carry a certain amount of
Sr, which may complicate origin determination. Besides
gypsum, CEM I can contain other constituents, included in
maximum 5% of minor additional constituents. Since they may
have an inuence on the Sr isotopic ngerprint, all the mineral
additions which are present in cement should be considered
while performing sample preparation. Furthermore, due to the
different fuels used in rotary kilns for clinker production, the
possible contribution regarding the contamination from fuels
must be assessed. Since only clinker carries the local raw
materials correlated to the Sr ngerprint and therefore the
origin, one must ensure that while preparing the sample, only
the clinker fraction is obtained. Finally, the measured isotope
ratios should correspond to those of the clinker fraction. To
exclude everything but the analyte while performing the
measurement, it is necessary to check and aerwards validate
the right analytical procedure, including matrix separation.
Another limitation of isotope analysis is the duration, which is
mainly attributed to the sample preparation. To isolate the
analyte of interest (e.g. Sr), matrix separation via cation-
exchange or extraction chromatography must be performed.
To date, the column preparation, resin cleaning and analyte-
matrix separation is being performed manually at the
expenses of working time. A few years ago, however, a new way
of fully automated sample purication system has been offered
as an option. The prepFAST MC® systems can overcome this
time-consuming issue in sample preparation.
119–123
An even
higher degree of automation might be allowed by laser ablation
coupled to ICP-MS when an automated sample changer and
corresponding soware packages are available.
Summary and outlook
Provenance studies of cement are of great importance for failure
research, damage assessment and resulting liability issues
related to concrete structures and in investigating ancient
building materials and in forensic science.
In this paper, the origin determination of cement has been
reviewed, and the main approaches from past and current
research have been presented. The majority of the published
work was related to trace elemental contents of cement and
clinkers, mostly combined with either the “star plot method”,
the “gray rational analysis”or other statistical and pattern
recognition methods. Even though the sample preparation and
the analysis presented in the publications were straightforward,
the data interpretation requires different visualisation
methods, such as star graphs to intuitively compare the data. An
advanced statistical method like PCA and clustering algorithms,
which require solid statistical knowledge and computational
power, restrict the number of potential users. Besides this, two
(Zn, V) from a maximum of eight elements have proven useless
because they originate from a fuel deployed in the production of
the clinker. Finally, the published literature revealed that
mostly clinkers were analysed. Clinker, however, only occurs
within the production process before other components are
admixed. Therefore, the provenancing of clinker is of almost no
practical relevance. The application of isotope ratios in the
provenancing of cement is scarce and is limited to Graham and
co-authors
48
and Kosednar-Legenstein and co-authors,
64,65
who
showed that Sr isotopes, combined with elemental analysis, are
useful tools for provenancing of cement in a restricted area
concerning time and space. When expanding this approach to
a larger region such as Europe or even worldwide, a second
isotope system is required to increase the resolution of the
provenancing approach. Here, Nd being another radiogenic
isotope system, is selected in addition to Sr. Both elements, Sr
and Nd, have their main occurrence in different components of
the raw mix of the cement. Thus, they act as tracers for different
raw materials. By measuring both Sr and Nd isotope ratios,
a characteristic isotopic ngerprint of cement can be estab-
lished, which then can be used to identify concrete of unknown
origin. The addition of the interelement ratio of Ca/Sr to the
strontium and neodymium isotope ratios will increase the
analytical resolution of the approach and most likely lead to the
geographical origin of the material, and ideally to its manu-
facturer. The main advantage of the Sr–Nd isotope analysis with
or without the Ca/Sr ratio over the statistical and pattern
recognition approaches is a reduced number of measurands
leading to a more straight forward statistical evaluation, which
can be visualized in 2D or 3D plots. The measurands them-
selves, the Sr and the Nd isotope ratio and the Ca/Sr ratio, show
a stronger correlation with the origin of the raw materials, thus
enabling a more precise mapping of the cement origin.
However, sample preparation needs to be improved to avoid
interferences from mineral additions that do not originate from
the clinker but also in terms of time consumption. The use of
automated matrix separation facilitates the sample preparation
and reduces chemicals as well as time consumption. Finally, the
expansion of the analytical approach, e.g. addition of Ca/Sr
ratios, needs to be considered to enable the transfer of this
approach to the provenance determination of concrete samples.
Future research should focus on three main topics: rst,
optimisation and validation of the proposed wet-chemical
method for cement provenancing should take place. Second,
an in situ method for the determination of
87
Sr/
86
Sr and
143
Nd/
144
Nd isotope ratios based on LA-ICP-MS should be
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developed for concrete provenancing. The lateral resolution of
LA should allow the differentiation between different mineral
phases of the concrete, i.e. the cementitious phase and the
aggregates. Together with the already determined isotope data
and the interelement ratios, the procedure for the determina-
tion of cement's origin should be transferable to concrete.
Third, a databank for isotopic ngerprints of cement should
be established. Besides answering individual questions
regarding the provenance of specic cement samples or
concrete structures, provenance studies also contribute to the
creation of cement datasets. Provenancing of cement allows the
complete documentation of the cement samples combining
isotope and concentration ratios along with their identied
provenance. As a result, new reference groups of various
cements of known origin are generated, while present ones
expand with new samples, leading to a reference databank.
Such a databank can be of great importance since it could
provide geochemists and other scientists with more knowledge
and could simplify future cement provenancing.
Abbreviations
AA Atomic absorption
AE Atomic emission
EDX Energy dispersive X-ray spectrometry
FGD Flue gas desulphurisation
ICP-MS Inductively coupled plasma mass spectrometry
ICP-
OES
Inductively coupled plasma optical emission
spectrometry
INAA Instrumental neutron activation analysis
IRMS Isotope ratio mass spectrometry
LA Laser ablation
LAMIS Laser ablation molecular isotopic spectrometry
MC Multi collector
OPC: ordinary Portland cement
PCA Principal component analysis
REE Rare earth elements
SC Single collector
SEM Scanning electron microscope
TIMS Multi collector thermal ionisation mass spectrometry
XRD X-ray diffraction
XRF X-ray uorescence
Author contributions
Anera Kazlagic: conceptualisation, methodology, project
administration, investigation, writing –original dra, writing –
review & editing, visualisation. Jochen Vogl: methodology,
supervision, funding acquisition, writing –original dra,
writing –review & editing. Gregor J. G. Gluth: methodology,
supervision, writing –review & editing. Dietmar Stephan:
methodology, supervision, writing –review & editing.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
The authors gratefully acknowledge the Federal Institute for
Material Research and Testing (BAM) for providing funds under
the project number MIT1-2019-8.
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