applied

sciences
Article
Carbon Dioxide Uptake by Cement-Based Materials:
A Spanish Case Study
Miguel Ángel Sanjuán 1, * , Carmen Andrade 2 , Pedro Mora 3 and Aniceto Zaragoza 4
1 Spanish Institute of Cement and its Applications (IECA), C/José Abascal, 53, 28003 Madrid, Spain
2 CIMNE–MADRID (UPC), P General Martínez Campos, 41, 9, 28010 Madrid, Spain; candrade@cimne.upc.edu
3 Department of Geological and Mines Engineering, Mine and Energy Engineering School, Technical
University of Madrid (UPM), C/Ríos Rosas, 21, 28003 Madrid, Spain; pedro.mora@upm.es
4 Oficemen, C/José Abascal, 53, 28003 Madrid, Spain; azaragoza@oficemen.com
* Correspondence: masanjuan@ieca.es; Tel.: +34-91-442-9166




Received: 12 December 2019; Accepted: 28 December 2019; Published: 2 January 2020


Featured Application: IPCC’s Guidelines for National Greenhouse Gas Inventories do not take
into account the net CO2 emissions due to the Portland cement clinker manufacturing; i.e., the
amount emitted as a consequence of the calcination process of the raw material in the clinker
production less the CO2 absorption occurred by the concrete carbonation. This article points out
that it is clear that the net assessment should be taken into account in the future climatic models.

Abstract: The European parliament has declared a global “climate and environmental emergency”
on 28 November 2019. Given that, climate change is a clear strategic issue all around the world.
Then, greenhouse gas emissions are reported by each country to the United Nations Framework
Convention on Climate Change (UNFCCC) every year. In addition, The Intergovernmental Panel on
Climate Change (IPCC) in the “2006 IPCC Guidelines for National Greenhouse Gas Inventories” give
the procedure to calculate and manage the national greenhouse gases (GHG) emissions. However,
these guidelines do not provide any method to consider the net carbon dioxide emissions to the
atmosphere (released in clinker fabrication minus those due to concrete carbonation) by the Portland
cement clinker industry. This topic should be implemented in the climatic models of the next IPCC
assessment report. This paper provides an easy procedure of estimating net CO2 emissions proposed
in the “recarbonation project” (simplified method); that is to say, carbon dioxide uptake during the
service-life stage is considered as the 20% of the CO2 released by the calcination (process emissions),
whereas the end-of-life and secondary usage is only the 3% of the CO2 released by calcination.
The outcome of this study reveals that 31,290.753 tons of carbon dioxide will be absorbed by the
cement-based materials produced in Spain with the cements manufactured from 2005 to 2015.

Keywords: climate emergency; climate change; climate models; carbon dioxide uptake; carbonation;
CO2 capture and utilization; cement industry; sustainability

1. Introduction
According to The Intergovernmental Panel on Climate Change (IPCC) [1,2], from 1750 until 2011,
the CO2 emissions coming from the use of fossil fuels and cement production released an average of
about 375 GtC year−1 (from 345 to 405). Between 2002 and 2011, the average emission of fossil fuels and
cement production stood at 8.3 GtC year−1 (from 7.6 to 9.0), showing an annual growth of 3.2%, which
is greater than what was recorded in the 1990s, which was 1%. In 2011 alone, the fossil fuel emissions
amounted to 9.5 GtC year−1 (from 8.7 to 10.3) [2]. Figure 1 shows the anthropogenic world emissions of
greenhouse gases (GHG) by economic sectors. It must be pointed out that the anthropogenic emissions

Appl. Sci. 2020, 10, 339; doi:10.3390/app10010339 www.mdpi.com/journal/applsci

Appl. Sci. 2020,
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Appl. Sci. 10, 339
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2020, 10,x xFOR
10, FORPEER
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anthropogenicworld
anthropogenic worldemissions
emissionsofofgreenhouse
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gases(GHG)
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Figure 1. World
Figure
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1.1.World
World of greenhouse-effect
emissions
emissions ofofgreenhouse-effectgases
greenhouse-effect gases(GHG)
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[2].
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Figure 2.2.World
2. World World emissions
emissions
emissions ofgreenhouse
of of greenhouse
greenhouse gases(GHG)
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(GHG) bysectors,
by sectors,inin
sectors, gigatons
ingigatons ofofof
gigatons CO
CO equivalent
2 2equivalent
CO 2 equivalent
annually
annually
annually [2].
[2]. [2].

Theeconomic
The
The economic economic
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sectors that
thatthat
most most
most affect
affect
affect the
thethe direct
direct
direct world
world
world emissions
emissions
emissions ofof
of greenhousegases
greenhouse
greenhouse gases(GHG)
gases (GHG) are
(GHG)
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are theelectricity
electricityand andheat
heatproduction
production(25%),(25%),industry
industry(21%),
(21%),and andtransport
transport(14%).(14%).All
Allofofthem
them
the electricity and heat production (25%), industry (21%), and transport (14%). All of them represent
represent 60% of the global direct GHG emissions (Figure 1). In particular, the effect
represent 60% of the global direct GHG emissions (Figure 1). In particular, the effect of the electricity, of the electricity,
60% of the global direct GHG emissions (Figure 1). In particular, the effect of the electricity, heat
heatproduction,
heat production,and andtransport
transport(39%)
(39%)could
couldbebereduced
reducedby bymeans
meansofoftechnological
technologicalimprovements
improvements
production, and
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transport
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gases(GHG) With regard to
(GHG)isisa asensitive
sensitive
the industrial
matter. sector, such reduction of emissions of greenhouse gases (GHG) is a sensitive matter.
matter.
On the other hand, indirect emissions of greenhouse gases (GHG) are mainly due to buildings
(12%) and industry (11%). Considering together direct and indirect emissions of both economic sectors,
the impact of buildings (18.4%) and industry (32%) became of great significance.
Figure 2 shows the evolution of the world emissions of greenhouse gases (GHG) from 1970 to 2010
by economic sectors. In the last decade (2000–2010), the increase in emissions attributed to industry
 Appl. Sci. 2020, 10, x FOR PEER REVIEW 3 of 16

Appl. Sci. 2020, 10, 339 3 of 16

On the other hand, indirect emissions of greenhouse gases (GHG) are mainly due to buildings
(12%) and industry (11%). Considering together direct and indirect emissions of both economic
sectors, the impact of buildings (18.4%) and industry (32%) became of great significance.
(+45%) and energy (+36%) was higher than three quarters (+81%). These data suggest the need to
Figure 2 shows the evolution of the world emissions of greenhouse gases (GHG) from 1970 to
implement technological measures to reduce the mentioned emissions.
2010 by economic sectors. In the last decade (2000–2010), the increase in emissions attributed to
In order(+45%)
industry to register the contribution
and energy of the than
(+36%) was higher European countries
three quarters to the
(+81%). EU record
These of emissions,
data suggest the
the Union’s registers guarantee exact accounting of all the emission
need to implement technological measures to reduce the mentioned emissions. rights allocated as a result of the
EuropeanInUnion Emissions
order to Trading
register the System
contribution of (EU ETS). The
the European registertokeeps
countries the EUa record
recordofofemissions,
the ownership
the of
the emission rights that
Union’s registers appear in
guarantee exacttheaccounting
electronic accounts in the same
of all the emission way
rights that a bank
allocated as a keeps a record
result of the of
European
customers andUnion
their Emissions
respectiveTrading
funds. System (EU ETS). The register keeps a record of the ownership
of
The theEuropean
emission Union
rights that appear in the
Transactions Logelectronic accounts in thechecks,
(EUTL) automatically same way that a and
records, bankauthorizes
keeps a all
record of customers and their respective funds.
the operations between union account records. This guarantees that all the transfers comply with the
The European Union Transactions Log (EUTL) automatically checks, records, and authorizes all
EU ETS standards. The EUTL is the successor to the Community Independent Transaction Log (CITL),
the operations between union account records. This guarantees that all the transfers comply with the
which performed the same function before the union register was introduced.
EU ETS standards. The EUTL is the successor to the Community Independent Transaction Log
The data
(CITL), contained
which in the
performed the union recordsbefore
same function includethethe
union31 register
countries wasthat take part in the European
introduced.
Union Emissions Trading System (EU ETS), which is merely an online
The data contained in the union records include the 31 countries that take part database thatinstores the accounts
the European
of holders
Union of fixed installations.
Emissions Trading System According
(EU ETS),to the data,
which the Portuguese
is merely an onlineindustry
database subject to emission
that stores the
rightsaccounts
emittedof4.6 million
holders tons of
of fixed carbon dioxide
installations. in 2015
According (total
to the data,absolute gross CO
the Portuguese emissions
industry
2 subjectwithout
to
emission rights emitted 4.6 million tons of carbon dioxide in 2015 (total
biomass emissions), which is 31.25% less than in 2005 (6.7 million tons of carbon dioxide).absolute gross CO 2 emissions
without biomass emissions), which is 31.25% less than in 2005 (6.7 million tons of carbon dioxide).
2. Effect of Emissions on Atmospheric CO2 and Global Temperature
2. Effect of Emissions on Atmospheric CO2 and Global Temperature
Figure 3 shows the trends in the world average temperatures on the surface, land, and oceans
Figure 3 shows the trends in the world average temperatures on the surface, land, and oceans
combined between 1850 and 2012 [1]. It is evident that from 1950 up to now, there is an increase in the
combined between 1850 and 2012 [1]. It is evident that from 1950 up to now, there is an increase in
world average temperatures on the surface, land, and oceans.
the world average temperatures on the surface, land, and oceans.

Figure
Figure 3. Irregularity
3. Irregularity observedininthe
observed theworld
world average
average temperatures
temperaturesonon
thethe
surface, landland
surface, and and
oceans
oceans
combined between 1850 and 2012 (Reproduced with permission from The Intergovernmental
combined between 1850 and 2012 (Reproduced with permission from The Intergovernmental Panel
Panel on
Climate Change, IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The Physical Science
Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on
Climate Change; Figure SPM.1 (a) Observed global mean combined land and ocean surface temperature
anomalies, from 1850 to 2012 from three data sets. annual mean values. published by Cambridge
University Press [1]).
 on Climate Change, IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The Physical Science
Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on
Climate Change; Figure SPM.1 (a) Observed global mean combined land and ocean surface
temperature anomalies, from 1850 to 2012 from three data sets. annual mean values. published by
Appl. Sci. 2020, 10, 339 4 of 16
Cambridge University Press [1]).

The sea surface temperature is a climate change indicator that increased during the 20th century
The sea surface temperature is a climate change indicator that increased during the 20th century
and continues to rise. From 1901 through 2015, the temperature rose at an average rate of 0.07 °C per
and continues to rise. From 1901 through 2015, the temperature rose at an average rate of 0.07 ◦ C per
decade. Sea surface temperature has been particularly higher during the last 30 years than at any
decade. Sea surface temperature has been particularly higher during the last 30 years than at any other
other period since 1880. Apparently, sea surface temperature appears to have cooled between 1880
period since 1880. Apparently, sea surface temperature appears to have cooled between 1880 and 1910.
and 1910. Nevertheless, it increased particularly between 1910 and 1940 and from 1970 to the present.
Nevertheless, it increased particularly between 1910 and 1940 and from 1970 to the present. Finally,
Finally, it should be considered that changes in sea surface temperature vary regionally. Given that,
it should be considered that changes in sea surface temperature vary regionally. Given that, some few
some few areas have experienced cooling, whereas most of the world’s oceans have reported
areas have experienced cooling, whereas most of the world’s oceans have reported temperature rise.
temperature rise.
In addition, global land temperature is considered as a climate change indicator. In this respect,
In addition, global land temperature is considered as a climate change indicator. In this respect,
2015 was the warmest year, and 2006–2015 the warmest decade reported worldwide since 1880
2015 was the warmest year, and 2006–2015 the warmest decade reported worldwide since 1880
(Figure 3). In addition, the global average surface temperature has risen at an average rate of 0.08 ◦ C
(Figure 3). In addition, the global average surface temperature has risen at an average rate of 0.08 °C
per decade since 1901.
per decade since 1901.
Carbon dioxide, CO2 , is a gas that exists in the air in a proportion of 0.03–0.04% in volume.
Carbon dioxide, CO2, is a gas that exists in the air in a proportion of 0.03–0.04% in volume.
Figure 4 shows the way that this gas has evolved historically in the atmosphere ranging from 280 ppm
Figure 4 shows the way that this gas has evolved historically in the atmosphere ranging from 280
in the preindustrial era to 400 ppm at the present time. Therefore, the rate at which this gas increases in
ppm in the preindustrial era to 400 ppm at the present time. Therefore, the rate at which this gas
the atmosphere is around 1–2 ppm/year. The data to obtain such conclusions come from ice core studies
increases in the atmosphere is around 1–2 ppm/year. The data to obtain such conclusions come from
and recent air monitoring measurements. In addition, global atmospheric concentrations of methane,
ice core studies and recent air monitoring measurements. In addition, global atmospheric
nitrous oxide, and other manufactured greenhouse gases have risen over the last years. Obviously,
concentrations of methane, nitrous oxide, and other manufactured greenhouse gases have risen over
the current global atmospheric concentrations of carbon dioxide are soared to unprecedented levels
the last years. Obviously, the current global atmospheric concentrations of carbon dioxide are soared
compared with the last years.
to unprecedented levels compared with the last years.

Figure 4. World carbon cycle: concentrations of carbon dioxide in the atmosphere [3].

It is well
well known
known that
that the
the carbon
carbon dioxide
dioxide concentrations
concentrations have increased significantly since the
beginning of the industrial era. Carbon dioxide concentrations
concentrations have
have risen
risen from 280 ppm in the late
1700s to
to 401
401 ppm
ppm inin 2015,
2015, as
as reported
reported recently
recently in
in some
some places.
places. This huge increase (43%) is attributed
mainly to human activities.
The most abundant greenhouse gas (GHG) in the atmosphere is the water vapor. However, the
human
human activities
activitieshave
haveaasmall
smalldirect
directinfluence onon
influence thethe
water vapor
water atmospheric
vapor atmosphericconcentrations. On the
concentrations. On
contrary, the human
the contrary, activitiesactivities
the human have a clear indirect
have a clearinfluence through
indirect irrigation
influence and deforestation.
through irrigation and
deforestation.
3. Carbon Dioxide Emissions by the Cement Sector
3. Carbon Dioxide
Currently, Emissions
cement by the
production Cement Sector
is considered as responsible for approximately 7.4% of the global
carbon dioxide emission (2.9 Gtons in 2016). Thus, the cement industry will play a key role in reducing
carbon dioxide emissions to minimize climate change. The cement industry has hugely reduced the
carbon dioxide emissions per ton of cement from the last century (Figure 5) [4,5], but the cement
production is growing worldwide due to the economic growth, notably in developing countries.
 Currently, cement production is considered as responsible for approximately 7.4% of the global
carbon dioxide emission (2.9 Gtons in 2016). Thus, the cement industry will play a key role in
reducing carbon dioxide emissions to minimize climate change. The cement industry has hugely
reduced the carbon dioxide emissions per ton of cement from the last century (Figure 5) [4,5], but
Appl. Sci. 2020, 10, 339
the
5 of 16
cement production is growing worldwide due to the economic growth, notably in developing
countries.
Japan
1%
Asia (without India
China, Japón 6%
e India)
21%

China
52%
Africa
5%
USA
2%
Latin America
5%
Pacific OCDE
0% CIS Rest of Europe Europe (CEMBUREAU)
3% 0% 5%

FigureFigure 5. World
5. World cement
cement production
production inby
in 2016 2016 by region
region and main
and main countries
countries (4.65[4].
(4.65 Gt) Gt) [4].

InIn2016, thethe
2016, worldwide cement
worldwide production
cement was about
production was 4.65 Gt (Figure
about 4.65 Gt5)(Figure
[4], where China
5) [4], produced
where China
52% and the 52%
produced rest of Asia
and produced
the rest of 28.5% of the world’s
Asia produced 28.5%production. Europeproduction.
of the world’s (The European Cement
Europe (The
Association (CEMBUREAU) members) only manufactures 5.3% of the world’s
European Cement Association (CEMBUREAU) members) only manufactures 5.3% of the world’s cement. Several CO 2
management approaches have been used in the last years in order to lower the climatic
cement. Several CO2 management approaches have been used in the last years in order to lower the change impact
and according
climatic to the
change project
impact anddeveloped
accordingby tothe
theWorld
projectBusiness Council
developed by theforWorld
Sustainable Development
Business Council for
and the Cement Sustainability Initiative (WBCSD-CSI) named “Getting the Numbers
Sustainable Development and the Cement Sustainability Initiative (WBCSD-CSI) named “Getting Right” (GNR),
The European Union (EU28) cement industry has significantly decreased the
the Numbers Right” (GNR), The European Union (EU28) cement industry has significantlyenvironmental impact [5].
Table 1 shows
decreased thesuch sharp decline
environmental from [5].
impact 2005Table
to 2015.
1 shows such sharp decline from 2005 to 2015.

Table
Table1. 1.Objectives
Objectivestotodecrease
decreasethe carbon
the dioxide
carbon emissions
dioxide inin
emissions the European
the cement
European industry
cement [5].
industry [5].
CarbonEmissions
Carbon Dioxide Dioxide Emissions Reduction
Reduction (Per (Per or Cementitious)
Ton of Clinker Grey Clinker Cementitious
Grey Clinker Cementitious
Ton of Clinker or Cementitious)
Gross carbon dioxide emissions −9% Data −13%
Net carbon
Gross carbon dioxide
dioxide emissions
emissions −9% −17%
Data −13% −21%
Net carbon dioxide emissions −17% −21%
Carbon dioxide emissions per ton of clinker are approximately about 825–890 kg CO2 (Figure 6)
[5], when a modern clinker kiln technology is considered. The worldwide average is about 840 kg
Carbon dioxide emissions per ton of clinker are approximately about 825–890 kg CO2 (Figure 6) [5],
CO2. Nevertheless, the medium-term target on carbon dioxide emission levels should be lower than
when a modern clinker kiln technology is considered. The worldwide average is about 840 kg CO2 .
400 kg per ton of cement. Emission levels of around 350–410 kg per ton of cement have been
Nevertheless, the medium-term target on carbon dioxide emission levels should be lower than 400 kg
suggested [6]. The cement industry is working hard to achieve this target by increasing clinker
per ton of cement. Emission levels of around 350–410 kg per ton of cement have been suggested [6].
substitution (production of blended cements), the use of alternative fuels and raw materials, and
The cement industry is working hard to achieve this target by increasing clinker substitution (production
thermal energy efficiency measures. Based on the use of the same technologies of clinker fabrication,
of blended cements), the use of alternative fuels and raw materials, and thermal energy efficiency
these measures will lead to lowering the global average carbon dioxide emissions from 630 kg CO2/t
measures. Based on the use of the same technologies of clinker fabrication, these measures will lead to
cement in 2015 to around 550 kg CO2/t cement in 2050, which is far away from the target threshold
lowering the global average carbon dioxide emissions from 630 kg CO2 /t cement in 2015 to around
level of 400 kg per ton of cement. In particular, García-Gusano et al. [7] suggested that the Spanish
550 kg CO2 /t cement in 2050, which is far away from the target threshold level of 400 kg per ton of
cement industry is able to lower the carbon dioxide emissions between 2010 and 2050 without
cement. In particular, García-Gusano et al. [7] suggested that the Spanish cement industry is able to
carbon capture and storage (CCS) by only 21%. Nevertheless, for this account, carbon dioxide uptake
lower the carbon dioxide emissions between 2010 and 2050 without carbon capture and storage (CCS)
by only 21%. Nevertheless, for this account, carbon dioxide uptake by the mortar and concrete should
be taken into account. The use of low CO2 -intensity cements combined with the consideration of the
carbon dioxide uptake by mortars and concretes will allow the sector to meet 550 kg CO2 /ton of cement
target in 2050.
Appl. Sci. 2020, 10, x FOR PEER REVIEW 6 of 16
Appl. Sci. 2020, 10, x FOR PEER REVIEW 6 of 16

by the mortar and concrete should be taken into account. The use of low CO2-intensity cements
by the mortar and concrete should be taken into account. The use of low CO2-intensity cements
combined with the consideration of the carbon dioxide uptake by mortars and concretes will allow
combined
Appl. with
Sci. 2020, the consideration of the carbon dioxide uptake by mortars and concretes will allow
10, 339 6 of 16
the sector to meet 550 kg CO2/ton of cement target in 2050.
the sector to meet 550 kg CO2/ton of cement target in 2050.
1000
1000

) )
/tClinker
975

/tClinker
975
950
CO2CO2
950
925
(kg(kg
925
900
intensity

900
intensity

875
875
850
2 emissions

850
2 emissions

825
825
800
800
Spain North America Africa
COCO

775 Spain North America Africa

775
Total

750 Middle East China-Korea-Japan Central America

Total

750 Middle East China-Korea-Japan Central America

725 EU 28 World
725 EU 28 World
700
7002004 2006 2008 2010 2012 2014 2016
2004 2006 2008 2010 2012 2014 2016

Figure 6. Gross carbon dioxide emissions for grey clinker from 2005 to 2015 [5].
Figure 6. Gross carbon dioxide emissions for grey clinker from 2005 to 2015 [5].
Figure 6 shows the gross carbon dioxide emissions for grey clinker from from 2005
2005 toto 2015.
2015. The gross
carbon Figure
dioxide 6 shows the gross
emissions arecarbon dioxide
the direct emissions
carbon dioxidefor emissions,
grey clinkerexcluding
from 2005 on-site
to 2015.electricity
The gross
carbon dioxide emissions,
carbon dioxide emissions
production, minus emissions are the direct carbon dioxide emissions, excluding on-site electricity
emissions from from biomass
biomass fuelfuel sources.
sources.
production,
Figure 7minus showsemissions from biomass fuel sources.
the CO 2 emissions
emissions due to the process and the combustion per ton of cement in
severalFigure 7 shows
countries fromthe COto
1990 2 emissions due to the process and the combustion per ton of cement in
2003 [8]. The weighted average of the carbon dioxide emissions is only
several
decreasing countries from 1990 to 2003 [8]. The
the weighted average ofare
theproposing
carbon dioxide emissions is only
decreasing atata aslow slowpace. On On
pace. one hand,
one hand, European countries
the European countries new cements
are proposing newincluding
cements
decreasing
aincluding
higher amount at a slow pace. On one hand, the European countries are proposing new cements
a higherofamount
additions, but on thebut
of additions, otheron hand, the USA,
the other hand, among
the USA, other countries,
among other continues
countries,
including
using mainlya higher
OPC amount
with OPCa very of additions,
high but
clinker/cementon the other hand,
ratio. The ratio. the
effort The USA,
made among
in the other countries,
European countries
continues using mainly with a very high clinker/cement effort made in the European
continues
is reflectedisusing
in Themainly
EuropeanOPC with a very high
Prestandard prEN clinker/cement
197-1:2019 ratio.
with theThe effort made of
incorporation in new
the European
types of
countries reflected in The European Prestandard prEN 197-1:2019 with the incorporation of new
countries For
cements.
is reflected
instance,
inGermany
The Europeanhas
Prestandard
reduced the
prEN 197-1:2019
clinker/cement ratio
with the incorporation
dramatically in the last
ofyears
new
types of cements. For instance, Germany has reduced the clinker/cement ratio dramatically in the
types of
(green
cements.
line(green
in Figure
For instance, Germany has reduced the Iclinker/cement ratio dramatically in the
the
last years line 7). This country
in Figure 7). Thisiscountry
reducing the CEM the
is reducing production, while at the
CEM I production, whilesame time
at the same
last years (green line in Figure 7). This country is reducing the CEM I production, while at the same
CEM II production
time the CEM II productionincreases. AnotherAnother
increases. good example is foundisinfound
good example the Spanish data (light
in the Spanish datablue
(lightline in
blue
time the CEM II production increases. Another good example is found in the Spanish data (light blue
Figure 7). In the year 1996, the Spanish emissions were
line in Figure 7). In the year 1996, the Spanish emissions were lower than 0.8 lower than 0.8 kg CO 2 per ton of cement
kg CO2 per ton of as
line in Figure 7). In the year 1996, the Spanish emissions were lower than 0.8 kg CO2 per ton of
acement
consequence of using siliceous
as a consequence fly ash,
of using natural pozzolan,
siliceous blast-furnace
fly ash, natural slag, and
pozzolan, limestone as
blast-furnace cement
slag, and
cement as a consequence of using siliceous fly ash, natural pozzolan, blast-furnace slag, and
constituents. Currently, this parameter is
limestone as cement constituents. Currently, this parameterabout 0.7 kg CO 2 per ton of cement. This trend is
is about 0.7 kg CO2 per ton of cement. good and
limestone as cement constituents. Currently, this parameter is about 0.7 kg CO2 per ton of cement.
could be improved
This trend is good and in the coming
could years. in the coming years.
be improved
This trend is good and could be improved in the coming years.
1000
1000
) )
Cl i nker

950
/tCl/ti nker

950
CO2CO2

900
(kg(kg

900
China
intensity

850 China
intensity

850 Korea
Korea
800 Japan
800 Japan
2 emissions

Canada
2 emissions

750 Canada
750 Germany
Germany
700 Spain
COCO

700 Spain
World
Total

650 World
Total

650
600
6001989 1991 1993 1995 1997 1999 2001 2003 2005
1989 1991 1993 1995 1997 1999 2001 2003 2005
Year
Year
Figure 7. CO2 emissions due to the calcination process and the combustion per ton of cement in some
countries [8].
 Appl. Sci. 2020, 10, x FOR PEER REVIEW 7 of 16

Figure
Appl. Sci. 7. CO
2020, 10, 339 2 emissions due to the calcination process and the combustion per ton of cement in some
7 of 16
countries [8].

Finally,
Finally,Figure
Figure8 8provides
providesinformation
informationononthe
thedirect
directcarbon
carbondioxide
dioxideemissions
emissionsdue
duetotothe
thecement
cement
production in the period from 1970 to 2050. In addition, the figure shows the prediction
production in the period from 1970 to 2050. In addition, the figure shows the prediction in carbon in carbon
dioxide
dioxideemissions
emissionsininthe thecoming
comingdecades
decadeswith
withthethecorrected
correctedtrend
trendififactions
actionson
oncarbon
carboncapture
capturewere
were
undertaken
undertaken[9].[9].

Figure8.8.Direct
Figure DirectCO
CO2 2emissions
emissionsdue
duetotocement
cementproduction
production(1970–2050)
(1970–2050)[9].
[9].

InInthe
theyear
year1970,
1970,500
500million
milliontonstonsofofcarbon
carbondioxide
dioxideemissions
emissionswere werereported
reportedby bythe thecement
cement
industry.
industry. Carbon dioxide emissions have more than doubled during the period from 1970toto2000.
Carbon dioxide emissions have more than doubled during the period from 1970 2000.
The
Thecement
cementindustry
industryhas hastrebled
trebleditsitscarbon
carbondioxide
dioxideemissions
emissionsininthethelast
last4040years
years(from
(from1970
1970toto2010).
2010).
The
Theprediction
predictioninincarbon
carbondioxide
dioxideemissions
emissionsininthe thecoming
comingdecades
decadeswill willdepend
dependon onthethedegree
degreeofof
implementation of carbon capture and storage (CCS) techniques in
implementation of carbon capture and storage (CCS) techniques in the cement sector. the cement sector.
Carbon
Carboncapture
captureand andstorage
storage(CCS)
(CCS)isisa atechnology
technologythat thatcan
cancapture
capturecarbon
carbondioxide
dioxideemissions
emissions
produced
produced from the calcination and the use of fossil fuels in the clinker kiln, preventingthe
from the calcination and the use of fossil fuels in the clinker kiln, preventing thecarbon
carbon
dioxide
dioxidefrom entering
from the atmosphere.
entering the atmosphere. Furthermore, the usethe
Furthermore, of carbon
use ofcapture
carbon and storageand
capture techniques
storage
with renewable
techniques withbiomass is a type
renewable of carbon
biomass abatement
is a type of carbontechnology.
abatement That is, it can
technology. be used
That to remove
is, it can be used
carbon
to remove carbon dioxide from the atmosphere. In particular, capture technologies of
dioxide from the atmosphere. In particular, capture technologies allow the separation carbon
allow the
dioxide fromof
separation gases produced
carbon dioxide in from
the clinkerization
gases produced process by pre-combustion
in the capture,by
clinkerization process post-combustion
pre-combustion
capture,
capture,and/or oxyfuel combustion.
post-combustion capture, and/or oxyfuel combustion.
4. Carbon Dioxide Uptake by Concrete
4. Carbon Dioxide Uptake by Concrete
Most of the carbon dioxide emissions from the Spanish Portland cement industry come from the
Most of the carbon dioxide emissions from the Spanish Portland cement industry come from
calcination of limestone (60–64%) rather than from fuel combustion. On the other hand, part of these
the calcination of limestone (60–64%) rather than from fuel combustion. On the other hand, part of
emissions is uptake by the mortar and concrete due to their carbonation during their exposition to the
these emissions is uptake by the mortar and concrete due to their carbonation during their
environment. The chemistry of carbonation has been reviewed in many papers [10–12]. In summary,
exposition to the environment. The chemistry of carbonation has been reviewed in many papers [10–
carbonation is produced because carbon dioxide is a gas present in the atmosphere that penetrates
12]. In summary, carbonation is produced because carbon dioxide is a gas present in the atmosphere
throughout the capillary pore network of concretes and mortars, where it is dissolved in the pore
that penetrates throughout the capillary pore network of concretes and mortars, where it is
solution and reacts with calcium ions [10] and other alkaline species [11,12] produced by the Portland
dissolved in the pore solution and reacts with calcium ions [10] and other alkaline species [11,12]
cement paste. Calcium carbonate has a very low solubility; then, it precipitates. With regard to the
produced by the Portland cement paste. Calcium carbonate has a very low solubility; then, it
pozzolanic constituents present in the cement as well as ground granulated blast-furnace slag, they
precipitates. With regard to the pozzolanic constituents present in the cement as well as ground
decrease the amount of calcium hydroxide in the binder due to the lower content in clinker when
granulated blast-furnace slag, they decrease the amount of calcium hydroxide in the binder due to
they are used, but they increase the amount of C-S-H gel. In addition, they lower the Ca/Si ratio of
the lower content in clinker when they are used, but they increase the amount of C-S-H gel. In
the C-S-H gel [13]. Consequently, the amount of calcium hydroxide that is able to be carbonated and
addition, they lower the Ca/Si ratio of the C-S-H gel [13]. Consequently, the amount of calcium
the composition of the C-S-H gel depend on the type and amount of the cement constituents (fly ash,
hydroxide that is able to be carbonated and the composition of the C-S-H gel depend on the type and
natural pozzolana, ground granulated blast-furnace slag, and so on) [14]. Additionally, blast-furnace
amount of the cement constituents (fly ash, natural pozzolana, ground granulated blast-furnace slag,
slag has some components that contribute to the carbon dioxide uptake by the Portland cement paste
and so on) [14]. Additionally, blast-furnace slag has some components that contribute to the carbon
Appl. Sci. 2020, 10, 339 8 of 16

present in mortars and concretes [15]. Therefore, the carbonation increases in cement-based materials
with ground granulated blast-furnace slag [16,17] in relation to their clinker content.
Some studies have been performed to determine the carbon dioxide uptake in order to ensure
a better carbon dioxide emissions balance. For instance, a Swiss study estimated that about 9.4–10.1%
of the calcination and fuel carbon dioxide emissions of the Portland cement utilized in 2010 [18] were
uptake during the concrete structures’ service life. This means that about 6% of the carbon dioxide
emissions coming from the calcination were uptake (considering that the ratio of the carbon dioxide
emission from calcination and fuel is 60:40).
A worldwide study has estimated a carbon dioxide uptake of 43% of the CO2 emissions from the
production of Portland cement by concretes and mortars from 1930 to 2013 [19]. This study considers
the service life period, end-of-life stage, and secondary use after demolition. In addition, it assumes
a degree of carbonation of about 80% in the carbonated area. Other papers suggested a full carbon
dioxide uptake (100% uptake) of the one emitted by calcination [20,21].
However, more conservative studies proposed lower carbon dioxide uptake levels [22–24].
A previous Spanish project reported much lower carbon dioxide uptake values (3–4%) as a consequence
of the lower surface/volume ratio considered (S/V = 3) in the concrete elements for a degree of
carbonation measured at one year of exposure [25]. These results were updated to 10.8–11.2% of
the carbon dioxide produced annually during the calcination process, considering the degree of
carbonation measured after four years of exposure [15].
The present paper covers some background of carbon dioxide uptake and also includes the results
of the simplest method proposed by the “recarbonation project” sponsored by The Portland Cement
Association (PCA), The European Cement Association (CEMBUREAU), The Cement Sustainability
Initiative (CSI), and Cementa in 2018 [26]. This methodology is applied to the cement-based materials
used in Spain first during their service life, and secondly, after the end-of-life and secondary usage stages.

5. Methodology
The method followed to calculate the carbon dioxide uptake by the Spanish cement industry
is the one proposed by the “recarbonation project” sponsored by The Portland Cement Association
(PCA), The European Cement Association (CEMBUREAU), The Cement Sustainability Initiative (CSI),
and Cementa in 2018 [26]. This procedure provides a simplified calculation for estimating the annual
uptake of CO2 in concrete during its use stage on a national basis. In this paper, the annual uptake in
the end-of-life stage and secondary use is also considered. The annual carbon dioxide uptake (ACDU)
values are related to the reported calcination CO2 emissions. Therefore, yearly carbon dioxide uptake
in the use stage has been calculated by applying Equation (1) and during the end-of-life and secondary
use by applying Equation (2). Based on the study performed by the IVL [26], we have considered the
following α and β parameters: α = 0.20 and β = 0.03.

ACDU (service life) = α × IPCC reported calcination emissions (1)

ACDU (end-of-life) = β × IPCC reported calcination emissions (2)

Such a method has been applied to the cements produced in Spain from 2005 to 2015, independently
of their final use.

6. Results and Discussion

6.1. Maximum Amount of Carbon Dioxide that Can Be Absorbed

The maximum amount of carbon dioxide that can be absorbed according to EN [27] is calculated
by applying Equation (3), and the result is shown in Table 2.

CO2,max = (CaOreactive /100) × binder × (MCO2 /MCaO ) (3)

Appl. Sci. 2020, 10, 339 9 of 16

where CO2,max : maximum amount of carbon dioxide that can be absorbed, kg CO2 /kg cement;
CaOreactive : kg CaO/kg binder × 100, and this value is taken as 65% (average value of the Spanish
clinkers); binder: amount of cement (kg); MCO2 : 44.0 g/mol; MCaO : 56.1 g/mol.
However, it does not consider the possible carbonation of other Portland cement components [11,12]
such as the alkaline compounds forming alkaline carbonates Equation (4).

CO2,max = (MCO2 /MCaO ) × (CaO − 0.7 × (SO3 )CaSO4 ) + (MCO2 /MNa2O ) × Na2 O + (MCO2 /MK2O ) × K2 O (4)

where CaO: kg CaO/kg Portland cement × 100; 0.7 × (SO3 )CaSO4 : kg CaO released from CaSO4 /kg
Portland cement × 100; Na2 O: kg Na2 O/kg Portland cement × 100; K2 O: kg K2 O/kg Portland cement ×
100; MCO2 : 44 g/mol; MCaO : 56 g/mol; MNa2O : 62 g/mol; and MK2O : 94 g/mol.
If we apply Equation (3) to a CEM I with 95% clinker that contains 65% CaO reagent, it holds that
the maximum amount of carbon dioxide that can be absorbed, according to EN, is equal to CO2,max
= (65/100) × 0.95 × (44/56) = 0.49 kg CO2 /kg CEM I. This value only applies to cement with 95%
clinker (CEM I) [28]. As far as other cements are concerned, this value will drop in proportion to
the clinker content. Table 2 has been prepared in order to be able to rapidly display the maximum
amount of carbon dioxide that the different can EN 197-1 cements could be absorb in theoretical and
unreal circumstances.
In fact, to calculate the maximum amount of carbon dioxide that can be absorbed for a cement,
it could be considered that 100% of the Ca (OH)2 of the portlandite (CH) and of the aluminates (AFt ,
AFm ) is carbonated, but only 50% of the C-S-H gel might be carbonated. Considering that in a cement
paste with 65.3% of CaO, 31.4% of such CaO is bound to C-S-H gel and the rest is bound to portlandite,
Ca(OH)2 , AFm and AFt phases, it would be necessary to take into account that only a maximum of 76%
of the CaO in the Portland cement clinker could be carbonated Equation (5).

CaO (carbonated) = 100 × (33.9/65.3) + 50 × (31.4/65.3) = 76% (5)

Fraction of the cement able to be carbonated = 0.76 × C × CaO × (MCO2 /MCaO ) (6)

where C: clinker content in the cement, kg clinker/kg Portland cement × 100; CaO: CaO content in the
Portland cement clinker (~0.65); MCO2 : 44 g/mol; and MCaO : 56 g/mol.
Appl. Sci. 2020, 10, 339 10 of 16

Table 2. Maximum amount of carbon dioxide, CO2 max , that the different cements (EN 197-1:2011) can absorb.

Minor Additional Factor Factor CO2,max ,

Main Types Type Name Type Notation Clínker, K
Constituents (Kcement /KCEM I ) (Kcement /KCEM I ) kg CO2 /tcement
CEM I Portland cement CEM I 95–100 0–5 95/95 = 1 1 490
80–88 0–5 80/95–94/95 0.84–0.99 410–480
Portland slag cement CEM II/A-S CEM II/B-S
65–79 0–5 65/95–79/95 0.68–0.83 340–410
Portland/silica fume cement CEM II/A-D 90–94 0–5 90/95–94/95 0.95–0.99 460–480
CEM II/A-P 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-P 65–79 0–5 65/95–79/95 0.68–0.83 340–410
Portland pozzolana cement
CEM II/A-Q 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-Q 65–79 0–5 65/95–79/95 0.68–0.83 340–410
CEM II/A-V 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-V 65–79 0–5 65/95–79/95 0.68–0.83 340–410
Portland–fly ash cement
CEM II CEM II/A-W 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-W 65–79 0–5 65/95–79/95 0.68–0.83 340–410
CEM II/A-T 80–94 0–5 80/95–94/95 0.84–0.99 410–480
Portland-burnt shale cement
CEM II/B-T 65–79 0–5 65/95–79/95 0.68–0.83 340–410
CEM II/A-L 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-L 65–79 0–5 65/95–79/95 0.68–0.83 340–410
Portland limestone cement
CEM II/A-LL 80–94 0–5 80/95–94/95 0.84–0.99 410–480
CEM II/B-LL 65–79 0–5 65/95–79/95 0.68–0.83 340–410
CEM II/A-M 80–88 0–5 80/95–94/95 0.84–0.99 410–480
Portland composite cement
CEM II/B-M 65–79 0–5 65/95–79/95 0.68–0.83 340–410
CEM III/A 35–64 0–5 35/95–64/95 0.37–0.67 180–330
CEM III Blast furnace cement CEM III/B 20–34 0–5 20/95–34/95 0.21–0.36 100–180
CEM III/C 5–19 0–5 5/95–19/95 0.05–0.20 30–100
CEM IV/A 65–89 0–5 65/95–89/95 0.68–0.94 340–460
CEM IV Pozzolanic cement
CEM IV/B 45–64 0–5 45/95–64/95 0.47–0.67 230–330
CEM V/A 40–64 0–5 40/95–64/95 0.42–0.67 210–330
CEM V Composite cement
CEM V/B 20–38 0–5 20/95–38/95 0.21–0.40 100–200
 CaO (carbonated) = 100 × (33.9/65.3) + 50 × (31.4/65.3) = 76% (5)

Fraction of the cement able to be carbonated = 0.76 × C × CaO × (MCO2/MCaO) (6)

where C: clinker content in the cement, kg clinker/kg Portland cement × 100; CaO: CaO content in the
Appl. Sci. 2020,
Portland 10, 339clinker
cement (~0.65); MCO2: 44 g/mol; and MCaO: 56 g/mol. 11 of 16

6.2. Carbon Dioxide Uptake by the Spanish Cements

6.2. Carbon Dioxide Uptake by the Spanish Cements
The amount of carbon dioxide that can be absorbed during the service life (Figure 9) of a
The amount of carbon dioxide that can be absorbed during the service life (Figure 9) of
product manufactured with cement is calculated with a fixed conservative value using the
a product manufactured with cement is calculated with a fixed conservative value using the simplified
simplified methodology. This value could either be 15% or 20% [27] of the CO2 emissions owing to
methodology. This value could either be 15% or 20% [27] of the CO2 emissions owing to the process
the process of calcination that is a long way from the maximum theoretical value of carbon dioxide
of calcination that is a long way from the maximum theoretical value of carbon dioxide that can be
that can be absorbed (around 490 kg of CO2 per tonne in the case of a cement without addition, CEM
absorbed (around 490 kg of CO2 per tonne in the case of a cement without addition, CEM I).
I).

Figure
Appl. Sci. 2020, 10, x FOR PEER 9. Circular economy in the cement production sector.
REVIEW sector. 11 of 16

The Spanish
The Spanish domestic
domestic data
data for
for CO22 emissions
emissions have
have been
been used
used to
to directly
directly apply
apply the simplified
methodology to estimate
methodology estimate CO
CO22 absorption
absorption(Figure
(Figure10).
10).Such
Suchemissions
emissionshave
havefallen
fallenfrom 2005
from to to
2005 2015 as
2015
a consequence
as of of
a consequence thethe
drop in clinker
drop production
in clinker (Figure
production 11).11).
(Figure

30,000,000
Absolute Gross Process CO2 Emissions (t)
Absolute CO2 Emissions (t)

25,000,000
Absolute Gross Fuel CO2 Emissions (t)
(without biomass emissions)
20,000,000

15,000,000

10,000,000

5,000,000

0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Figure 10. Absolute CO2 emissions (tons) evolution from 2005 to 2015 for the Spanish clinker production:
Figure 10. Absolute CO 2 emissions (tons) evolution from 2005 to 2015 for the Spanish clinker
process emissions (bars in blue); fuel emissions (bars in orange).
production: process emissions (bars in blue); fuel emissions (bars in orange).

35,000,000
Grey White
30,000,000
inker production (tons)

25,000,000

20,000,000

15,000,000
 0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Appl. Sci. 10, 339

2020, 10.
Figure 12 of 16
Absolute CO2 emissions (tons) evolution from 2005 to 2015 for the Spanish clinker
production: process emissions (bars in blue); fuel emissions (bars in orange).

35,000,000
Grey White
30,000,000
Clinker production (tons)

25,000,000

20,000,000

15,000,000

10,000,000

5,000,000

0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Figure
Figure 11. 11. Clinker
Clinker production
production (tons):
(tons): grey
grey clinker
clinker (bars
(bars in blue);
in blue); white
white clinker
clinker (bars
(bars in orange).
in orange).

Figure
Figure 12 12 evidences
evidencesthe thedecrease
decreaseofofthe the carbon
carbon dioxide
dioxide combustion
combustion emissions
emissions intensity
intensity fromfrom
336
336 kg CO2 /tclinker in 2005 to 308 kgCO2 /t clinker in 2015. In addition, the carbon dioxide
kgCO2/tclinker in 2005 to 308 kgCO2/tclinker in 2015. In addition, the carbon dioxide process emissions process emissions
intensity
Appl.
intensity from
Sci. 2020,
from10, 529
x FOR
529 kg
kgPEER /tclinker
CO2/tREVIEW
CO2 clinkerinin 2005
2005 toto 522kgkg
522 CO2
CO2
/tclinker
/tclinker in 2015.
in 2015. 12 of 16

1.0 CO2 process emissions intensity

0.9 CO2 combustion emissions intensity
CO2 emissions intensity (tCO2/tclinker)

0.8
0.7 0.336 0.333 0.334 0.334 0.319 0.314
0.302 0.298 0.290 0.303 0.308
0.6
0.5
0.4
0.3
0.529 0.522 0.525 0.527 0.528 0.528 0.522 0.524 0.522 0.525 0.522
0.2
0.1
0.0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Figure 12. CO global emissions intensity (t /tclinker ). Evolution from 2005 to 2015 of the Spanish
Figure 12. CO22 global emissions intensity (tCO2
CO2/tclinker). Evolution from 2005 to 2015 of the Spanish
clinker production.
clinker production.
The taxonomy report [29] proposes a limit value for clinker production of 766 kgCO2 /tclinker .
The taxonomy report [29] proposes a limit value for clinker production of 766 kgCO2/tclinker. This
This value is lower than the reported for the Spanish clinkers shown in Figure 12. Such report also
value is lower than the reported for the Spanish clinkers shown in Figure 12. Such report also
suggests threshold values for other parameters (clinker/cement ratio < 0.65; kgCO2 /tcement < 498, and
suggests threshold values for other parameters (clinker/cement ratio < 0.65; kgCO2/tcement < 498, and
kWh/tcement < 85). This proposal was presented with very strict limits on CO2 emissions and energy
kWh/tcement < 85). This proposal was presented with very strict limits on CO2 emissions and energy
demand in cement production. Therefore, it will be very difficult to meet in many cases, particularly in
demand in cement production. Therefore, it will be very difficult to meet in many cases, particularly
CEM I production [28].
in CEM I production [28].
All in all, if a factor of 0.20 is applied to the CO2 calcination emissions Equation (1) (which is what
All in all, if a factor of 0.20 is applied to the CO2 calcination emissions Equation (1) (which is
is proposed in the IVL simplified methodology [26]), given that, CO2 absorption in Spanish cement
what is proposed in the IVL simplified methodology [26]), given that, CO2 absorption in Spanish
manufacturing plants attributed to the service life period has been estimated at 27,358.481 tons of CO2
cement manufacturing plants attributed to the service life period has been estimated at 27,358.481
in the period from 2005 to 2015 (Figure 13). In a similar way, the CO2 absorption estimation during the
tons of CO2 in the period from 2005 to 2015 (Figure 13). In a similar way, the CO2 absorption
end-of-life and secondary use was calculated by using Equation (2), and the results are also given in
estimation during the end-of-life and secondary use was calculated by using Equation (2), and the
Figure 13.
results are also given in Figure 13.

4.5 Carbon dioxide uptake (20%) of the one emitted by calcination - MM tonnes
M tons)

Carbon dioxide uptake (3%) of the one emitted by calcination - MM tonnes

4.0

3.5
 All in all, if a factor of 0.20 is applied to the CO2 calcination emissions Equation (1) (which is
what is proposed in the IVL simplified methodology [26]), given that, CO2 absorption in Spanish
cement manufacturing plants attributed to the service life period has been estimated at 27,358.481
tons of CO2 in the period from 2005 to 2015 (Figure 13). In a similar way, the CO2 absorption
estimation
Appl. Sci. 2020,during
10, 339 the end-of-life and secondary use was calculated by using Equation (2), and the
13 of 16
results are also given in Figure 13.

4.5 Carbon dioxide uptake (20%) of the one emitted by calcination - MM tonnes

Carbon dioxide uptake (MM tons)

Carbon dioxide uptake (3%) of the one emitted by calcination - MM tonnes
4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0
2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015

Figure 13.
Figure Carbon dioxide
13. Carbon dioxide uptake
uptake by
by the
the cement-based
cement-based materials
materials produced
produced with
with the
the Spanish
Spanish cement
cement
manufactured between 2005 and 2015 considering the IVL simplified methodology [26].
manufactured between 2005 and 2015 considering the IVL simplified methodology [26].

The CO total amount for the end-of-life and secondary use between 2005 and 2015 is estimated
The CO22 total amount for the end-of-life and secondary use between 2005 and 2015 is estimated
at 3,932,272 tons of CO2 . Summing up, it can be said that the total amount of carbon dioxide uptake of
at 3,932,272 tons of CO2. Summing up, it can be said that the total amount of carbon dioxide uptake
the Spanish cement industry from 2005 to 2015 is 31,290,753 tons of CO2 (Figure 13).
of the Spanish cement industry from 2005 to 2015 is 31,290,753 tons of CO 2 (Figure 13).
Figure 13 shows the carbon dioxide uptake by the cement-based materials produced with the
Spanish cement manufactured between 2005 and 2015 considering the IVL simplified methodology [26].
(Only the CO2 emitted as a result of the decarbonation process is taken into account, i.e., emissions due
to fuel are not considered).
Climate models have been improved since the Fourth Assessment Report of the Intergovernmental
Panel on Climate Change (AR4). The ability of climate models to simulate temperature increase has
enhanced in many significant aspects, though not all. Given that, the climate models evaluated by
Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change
(AR5) do not take into account the net carbon dioxide emissions of the cement industry [30]. Therefore,
all the models can be improved by adding this parameter.

6.3. Carbon Dioxide Indicators for Concretes

Figure 14 collects the results of the kgcement /(m3 × MPa) indicator for 40 commercial concretes
made in Spain [31]. This indicator, among others, is proposed to measure the environmental impact
of the construction materials [29]. The results range from 5 to 14 kgcement /(m3 × MPa). Most of
the CEM I and half of the CEM II/A-V cements [28] range between 5 and 8 kgcement /(m3 × MPa).
As consequence, the higher the 28-day compressive strength, the lower the carbon dioxide indicator
defined as kgcement /(m3 × MPa). In addition, high-strength and high-performance concretes led to
the design of slender concrete elements than using normal concrete. Given that, a lower amount of
concrete is necessary. Consequently, it can be underlined that the global environmental impact of using
this type of concrete is lower.
Blended cements, which are recommended for aggressive environments because they are able
to provide a longer service life of the concrete structures, exhibited higher carbon dioxide indicator
values. Therefore, we share the view that the scientist should better suggest more adequate carbon
dioxide indicators in which the concrete durability would be seen as a capital aspect. In addition, new
cement types [32] and concrete designs [33] are developed in order to progress in accordance with the
climate change actions [34].
I and half of the CEM II/A-V cements [28] range between 5 and 8 kgcement/(m3 × MPa). As consequence,
the higher the 28-day compressive strength, the lower the carbon dioxide indicator defined as
kgcement/(m3 × MPa). In addition, high-strength and high-performance concretes led to the design of
slender concrete elements than using normal concrete. Given that, a lower amount of concrete is
necessary. Consequently, it can be underlined that the global environmental impact of using
Appl. Sci. 2020, 10, 339
this
14 of 16
type of concrete is lower.

14

Carbon dioxide indicator

(kg cement/(m3 x MPa))
12

10

6 CEM I
CEM II/A-V
4 CEM II/A-M
2 CEM III
CEM IV/A
0
0 20 40 60 80
28-days compressive strength (MPa)
Figure 14. Carbon dioxide indicator, kgcement /(m3 × MPa), for 40 Spanish commercial concretes.
Figure 14. Carbon dioxide indicator, kgcement/(m3 × MPa), for 40 Spanish commercial concretes.
Finally, it is believed that the net assessment with regard to the anthropogenic CO2 emissions of
Blended
the cement cements,
sector shouldwhich are into
be taken recommended for aggressive
account in future environments
climatic models because
due to the they are able
great significance of
to provide a longer service life of the concrete structures, exhibited higher carbon dioxide
the clinker production. For instance, in 2016, the estimated contribution of the cement industry to the indicator
values. Therefore,
anthropogenic CO2we share the
emissions wasview that
7.4% (2.9the scientist
Gtons CO2 )should
of worldbetter suggest
carbon more
dioxide adequate
emissions (39carbon
Gtons
dioxide indicators in which the concrete durability would be seen as a capital aspect.
CO2 ). However, if we take into account the CO2 uptake by applying the simplified methodology, In addition,
such
new cement types [32] and concrete designs [33] are developed
contribution is now estimated to be 6.3%, as shown in Equation (7). in order to progress in accordance
with the climate change actions [34].
Net CO2 emissions = (Total CO2 emissions) − (0.23 × Process CO2 emissions) (7)

where total CO2 emissions in 2016: 2.9 Gtons CO2 ; and process CO2 emissions in 2016: 0.64 × 2.9 Gtons
CO2 = 1.86 Gtons CO2 .
In this case, it is assumed that 64% of the total carbon dioxide emissions are due to the calcination
process. Therefore, the net CO2 emissions in 2016 are 2.47 Gtons CO2 .

7. Conclusions
The conclusions reached with this study are as follows:

• Carbon dioxide absorption attributed to the Spanish cements produced from 2005 to 2015 was
estimated at 31,290,753 tons when using the simplified methodology, i.e., applying a factor of 0.20
during the service life and 0.03 for the end-of-life and secondary use.
• The net carbon dioxide emissions related to the Portland cement clinker industry (CO2 released in
clinker fabrication minus CO2 uptake by concrete carbonation) should be implemented in the
climatic models of the next IPCC assessment report.
• This simplified model developed by experts in the mortar and concrete carbonation field should
be validated by each country. Thus, it will allow the national climate change offices to implement
these methodologies in the national greenhouse gas inventories.

Author Contributions: Conceptualization, C.A. and M.Á.S.; methodology, C.A. and M.Á.S.; software, M.Á.S.;
formal analysis, M.Á.S.; investigation, C.A. and M.Á.S.; resources, A.Z.; data curation, M.Á.S.; writing—original
Appl. Sci. 2020, 10, 339 15 of 16

draft preparation, M.Á.S.; writing—review and editing, A.Z., P.M., C.A., and M.Á.S.; visualization, A.Z. and P.M.,
supervision, P.M.; project administration, P.M.; funding acquisition, P.M. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by Oficemen.
Acknowledgments: The authors want to thank Commission C1 “Climatic change” of Oficemen for the support and
recommendations provided during the realization of this study. Authors also want to thank the Intergovernmental
Panel on Climate Change permission to publish Figure 3 (Figure SPM.1 (a) from IPCC, 2013: Summary for
Policymakers. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth
Assessment Report of the Intergovernmental Panel on Climate Change).
Conflicts of Interest: The authors declare no conflict of interest.

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