Vanhille 2016

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Construction and Building Materials 127 (2016) 26–29

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Construction and Building Materials


journal homepage: www.elsevier.com/locate/conbuildmat

Technical note

Application and verification of direct transesterification as a method


to quantify fatty acids in cement and concrete
Rob van Hille 1,⇑, Melinda Griffiths
Centre for Bioprocess Engineering Research (CeBER), Department of Chemical Engineering, University of Cape Town, Rondebosch 7701, Cape Town, South Africa

h i g h l i g h t s

 A modified direct transesterification method was developed to quantify fatty acids in concrete.
 The method was validated using cement treated with olive oil and milk.
 Both total and individual fatty acids were quantified.
 The method can be used to measure fatty acids used as phase change materials in ‘‘green” buildings.

a r t i c l e i n f o a b s t r a c t

Article history: Fatty acids are increasingly being evaluated as phase change materials to enhance thermal regulation in
Received 30 May 2016 buildings and as hydrophobic admixtures to reduce water ingress into concrete. This paper describes the
Received in revised form 6 September 2016 development of a method for the rapid and accurate quantification of fatty acids in cement and concrete.
Accepted 28 September 2016
The method is based on direct (in situ) transesterification of fatty acids into fatty acid methyl esters and
their subsequent extraction in a single step, followed by quantification by gas chromatography. The
method was validated using cement treated with olive oil and milk and showed a proportional relation-
Keywords:
ship between dosing and fatty acids quantified. This method provides an accurate alternative to existing
Phase change material
Admixture
qualitative procedures.
Fatty acids Ó 2016 Elsevier Ltd. All rights reserved.
Quantitative assay
Thermal regulation

1. Introduction chain consisting of an even number of carbon atoms. The general


formula for an unbranched, saturated fatty acid is CH3(CH2)nCOOH,
Concrete typically consists of aggregate, Portland cement, water where n can range from 2 to 26. All fatty acids have the carboxyl
and admixtures. Admixtures are an essential component of (-COOH) group at one end of the molecule. The group may be
modern concrete and although added in very small amounts, have deprotonated under certain conditions, generating a negatively
a profound impact on important properties of the material. The charged functional group that can interact with positively charged
majority of admixtures function by modifying interfacial proper- ions or functional groups.
ties, either solid-liquid or liquid-vapour [1]. The primary reasons The chemical structure and properties of fatty acids make them
for the addition of admixtures are to reduce cost, to achieve certain suitable for use as admixtures in concrete formulations. The
properties more effectively and to maintain quality during mixing, carboxyl group can be attracted to positively charged colloidal
transporting, placing and curing, particularly during adverse particles in concrete in a similar fashion to the carboxyl group in
weather conditions. polycarboxylate ether (PCE), a common superplasticizer [2].
Fatty acids are a group of carboxylic acids with a long, aliphatic Liquid-phase fatty acids have a sufficiently high surface tension
(hydrocarbon) chain, which is either saturated or unsaturated (2–3  104 N/m) for them to be retained within the composite
(contains double bonds). Most fatty acids have an unbranched material [3].
Previously, fatty acids have been investigated as grinding aid
⇑ Corresponding author. additives, but the results were not particularly encouraging [4].
E-mail addresses: rob@mossgroup.co.za (R. van Hille), melinda.griffiths@uct.ac. The study found that most of the fatty acids significantly decreased
za (M. Griffiths). the compressive strength, although myristic and stearic acids could
1
Present address: The Moss Group, 13 Bell Crescent, Westlake Business Park, Cape be used as grinding aids at concentrations below 0.1 wt%. Far more
Town, South Africa.

http://dx.doi.org/10.1016/j.conbuildmat.2016.09.149
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
R. van Hille, M. Griffiths / Construction and Building Materials 127 (2016) 26–29 27

promising applications for fatty acids are as a phase change mate- 2. Materials and methods
rial (PCM) to enhance thermal storage capacity in energy efficient
buildings and as hydrophobic admixtures to reduce water ingress. 2.1. Cement samples
The PCMs have been impregnated into a range of building materi-
als [5,6], including concrete, and function by absorbing or releasing The control material was based on a standard CEM1 mix, cast in
heat at different temperatures, as their phases change. Both inor- the Department of Civil Engineering. The samples were prepared
ganic (salts, metals, alloys) and organic (paraffins, alcohols, fatty by removing the aggregate material and pulverising the remaining
acids) PCMs have been investigated, but organic PCMs are pre- sample into a fine powder ( 75 lm). The decision to remove the
ferred due to their large latent heats and thermal characteristics aggregate was based on its limited porosity.
[2]. Fatty acids are particularly attractive as they are not derived Three unknown samples were obtained from the dairy product
from fossil fuels, are less flammable than paraffins and in certain warehouse. The epoxy coating was removed from the top and the
cases don’t require microencapsulation [7]. remaining drill core was divided into an upper and lower fraction.
The ingress of water is a significant contributor to all major The material was prepared in the same way as the control material,
physical and chemical degradation process affecting concrete by removing the aggregate and pulverising.
structures [8], either as the primary degrading agent (i.e. freeze/
thaw cycles [9]) or as a carrier for aggressive species, such as
chloride, that are responsible for corrosion. Traditional approaches 2.2. Method development
to reduce water ingress include employing a low water-cement
ratio, limiting crack widths and using supplementary cementitious The assay was developed by modifying the direct transesterifi-
materials, although the inherently porous nature of concrete limits cation technique developed by Griffiths [14] for the analysis of
the effectiveness. Alternative approaches include the use of lipid content in algae. Two internal standards were used. Glyceryl
integral water-resistant admixtures, which have advantages over triheptadecanoate (C17-triacyl glycerate) was added prior to the
surface protecting agents [8]. Hydrophobic agents, such as fatty reaction, as a quantitative internal standard and methyl nonade-
acids, fatty acid soaps, vegetable oils, wax emulsions, animal fats, canoate (C19-methyl ester) was added in the final solvent extrac-
silanes, siloxanes and hydrocarbons, alter the surface tension or tion step to verify the completeness of the transesterification.
surface energy within the pores and cracks [8–10]. This increases These were selected as standards as odd-numbered fatty acids do
the liquid contact angle and consequently reduces water ingress. not normally occur in nature, so are highly unlikely to be present
Currently, there are no standard protocols for the quantitative in the samples.
assessment of fatty acids in cement and concrete. Quantification The sample (20 mg pulverized concrete) was treated with
of the loss of fatty acids during repeated phase change cycles is 500 lL hexane, containing 0.1 mg of the C17-TAG standard, in a
critical in evaluating their potential as PCMs, given the lifespan
of most buildings. Cellat and co-workers [2] used a simple filter
20
paper test to quantify fatty acid loss, but were required to use a (a)
18
10 wt% loading, which is orders of magnitude greater than the typ-
Total fatty acids (mg)

ical loading, so there is definitely scope for a more sensitive tech- 16


nique, particularly one capable of differentiating between fatty 14
acids. 12
Traditionally, fatty acids have been quantified gravimetrically 10
or by chromatography, following solvent extraction [11]. More 8
accurate quantification of individual and total fatty acids is possi-
6
ble by gas chromatography (GC), but this requires derivatization
4
to generate volatile fatty acid methyl esters (FAMEs). This is nor-
mally achieved by converting saponifiable lipids, such as triacyl- 2
glycerols or phospholipids to FAME by the addition of an excess 0
0 5 10 15 20 25
of methanol and a catalyst, in a reaction known as transesterifica-
tion. Transesterification involves the cleaving of an ester bond by Volume of olive oil added (µL)
an alcohol (methanol) and can be catalysed by either an acid or a
base. Basic catalysts transesterify complex lipids quickly and at rel- 3.0
(b)
atively low temperature, but not free fatty acids, while acid cata-
lysts can work on both types, but require a longer reaction time 2.5
and an elevated temperature [12]. A combination of a basic cata-
Total fatty acids (mg)

lyst, followed by an acid catalyst may be used. 2.0


Transesterification eliminates the problem of the extraction of
non-fatty acid substances, but the accuracy remains dependent 1.5
on the completeness of the solvent extraction. The process can
be simplified by employing direct transesterification (DT), a simple
1.0
and rapid process that combines the transesterification and extrac-
tion steps into one [13]. The method described below was modified
0.5
from a DT process developed to quantify fatty acids in microalgae
[14].
While the method will be most appropriate for quantifying fatty 0.0
0 20 40 60 80 100 120
acids used as PCMs, it was originally developed to assess possible
fatty acid contamination of a concrete floor from a dairy product Volume of milk added (µL)
warehouse, which resulted in poor adhesion of an epoxy coating Fig. 1. Standard curves for control material treated with increasing volumes of (a)
added subsequently. Those data are presented in the results olive oil and (b) milk. Data points represent the mean values of assays in triplicate.
section. Standard deviation <2.5%.
28 R. van Hille, M. Griffiths / Construction and Building Materials 127 (2016) 26–29

Table 1
Fatty acid profiles extracted from control material treated with olive oil and milk, relative to published values. C:D refers to carbon number (C) and number of double bonds (D).

Acid name C:D Olive oil (% of total lipid) Milk (% of total lipid)
Experimental Published [15] Experimental Published [16]
Capric C10 2.0 2.4–3.5
Lauric C12 2.5 3.0–4.1
Myristic C14 10.1 10.0–12.1
Myristoleic C14:1 0.7 0.4–1.3
Palmitic C16 9.6 7.5–20 34.8 28.7–34.1
Palmitoleic C16:1 1.2 0.9–1.8
Sapienic C16:1 0.3
Stearic C18 3.7 0.5–5 13.6 10.3–13.3
Oleic C18:1 79.7 55–83 28.6 19.7–24.7
Linoleic C18:2 5.6 3.5–21 3.2 1.4–1.8

Table 2
Quantification and relative proportion of individual fatty acids extracted from the dairy warehouse concrete samples.

Acid name C:D Sample 1 top Sample 2 top


mg/g Relative% mg/g Relative%
Capric C10 0.85 3.9 1.16 3.8
Lauric C12 0.98 4.5 1.30 4.3
Myristic C14 3.07 14.0 3.80 12.5
Palmitic C16 7.51 34.3 9.25 30.3
Stearic C18 2.77 12.7 3.44 11.3
Oleic C18:1 6.72 30.7 7.76 25.5
Total fatty acid 21.87 30.55

glass test-tube with a silicon-lined screw cap. The basic catalyst, The unknown samples from the warehouse floor (20 mg) were
sodium methoxide (1 mL), was added and the sample was well subjected to the extraction and transesterification protocol
mixed by vortexing. The tube was incubated on a rotary shaker described above prior to GC analysis.
(300 rpm) at 80 °C for 20 min. The sample was then cooled to room
temperature and 1 mL of acid catalyst (BF3 methanol) added. The
sample was mixed and incubated as before. After cooling to room 3. Results and discussion
temperature, 400 lL deionised water and 400 lL hexane, contain-
ing 0.1 mg of the C19-ME standard, were added. The sample was 3.1. Method development and verification
mixed by vortexing, followed by centrifugation at 4000 rpm for
1 min. The upper hexane-toluene layer, containing any fatty acid The data for the control samples exposed to olive oil (Fig. 1(a))
methyl ester (FAME) extract, was transferred to vials for gas chro- and milk (Fig. 1(b)) show a linear relationship between the total
matography (GC). fatty acid quantified and the volume added to the sample. The R2
value for the olive oil was 0.951, with the first data point deviating
slightly. This can most likely be attributed to the challenge associ-
2.3. Gas chromatography analysis
ated with accurately pipetting 2 lL of viscous oil. The total fatty
acid value measured was appreciably higher for the olive oil, due
The FAME extract (1 lL), containing the internal standards, was
to the significantly lower fatty acid content of milk. For the milk
injected into a Varian 3900 GC equipped with a flame ionisation
treated samples, the R2 value was 0.995, confirming the repro-
detector and Supelco Wax 10 column (30 m  320 mm  1.0 lm
ducibility and high degree of accuracy of the analysis. The concrete
film thickness). Standard split/splitless injection was used with a
material did influence the efficiency of the transesterification, with
split of 100 and an injector temperature of 270 °C. The column
the total fatty acids quantified from the milk-treated samples rang-
temperature was increased from 180 °C to 260 °C at a rate of 2 °C
ing between 77% and 86% of the amount in the equivalent volume
per minute. Nitrogen (2 mL.min 1) was used as the carrier gas.
of milk, but this could be corrected for by assessing the values of
The detector temperature was set at 260 °C. Peaks were identified
the two internal standards.
by retention time using Supelco 37 component FAME and C14:0 to
The fatty acid profiles for the olive oil and milk treated samples
C22:0 FAME mixtures. Peak areas were used to quantify each FAME
are presented in Table 1. The dominant fatty acids and their rela-
relative to the internal standards. The relationship between peak
tive proportions are consistent with published data [15,16] and
area and concentration was consistent for all FAMEs tested so
the control analysis performed prior to treating the pulverized
the total lipid content was determined by adding the peak areas
concrete.
for all peaks.

2.4. Method verification and unknown sample analysis 3.2. Evaluation of experimental samples

The method was verified, in triplicate, by treating 20 mg sam- The analysis of the six concrete samples (sample 1–3, top and
ples of the control material with olive oil (known composition) bottom) showed that only the top fraction of samples 1 and 2 were
and milk in increasing volumes (10–100 lL). The samples were positive for lipid. For the other four samples, the only peaks on the
dried overnight prior to extraction. The relationship between the GC chromatogram corresponded to the two internal standards.
lipid detected and volume added was used to validate the assay. This confirmed that accuracy of the GC analysis and that the sam-
R. van Hille, M. Griffiths / Construction and Building Materials 127 (2016) 26–29 29

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