Sie sind auf Seite 1von 17

Analytica Chimica Acta 797 (2013) 6480

Contents lists available at ScienceDirect

Analytica Chimica Acta


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

Alkyd paints in art: Characterization using integrated mass


spectrometry
Jacopo La Nasa, Ilaria Degano, Francesca Modugno , Maria Perla Colombini
University of Pisa, Department of Chemistry and Industrial Chemistry, Via Risorgimento, 35, I-56126 Pisa, Italy

h i g h l i g h t s g r a p h i c a l a b s t r a c t

We characterized commercial alkyd


paints used in contemporary art.
We used a multi-analytical approach
based on mass spectrometry.
We present the rst application of
TAGs proling by HPLCESI-Q-ToF to
alkyd paints.
FIA-ESI-Q-ToF was tested for the rst
time for the analysis of alkyd paints.

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

Article history: Alkyd resins have been commonly used as binders in artist paints since the 1940s. The characterization
Received 23 April 2013 of alkyds in samples from artworks can help to solve attribution and dating issues, investigate decay pro-
Received in revised form 29 July 2013 cesses, and contribute to the planning of conservation strategies. Being able to assess the components of
Accepted 10 August 2013
industrially formulated paint materials and to differentiate between different trademarks and producers
Available online 20 August 2013
is extremely interesting and requires multi-analytical approaches.
In this paper we describe the characterization of commercial alkyd paint materials using a multi-
Keywords:
analytical approach based on the integration of three different mass spectrometric techniques: gas
Alkyd resins
Gas chromatography/mass spectrometry chromatographymass spectrometry (GC/MS), high performance liquid chromatography coupled with
High performance liquid chromatography electrospray ionization mass spectrometry with a tandem quadrupole-time of ight mass spectrometer
Electrospray ionization-quadrupole-time of (HPLCESI-Q-ToF), and ow injection analysis (FIA) in the ESI-Q-ToF mass spectrometer.
ight mass spectrometry GC/MS was successful in determining the fatty acid and aromatic fractions of the resins after hydrolysis;
Flow injection analysis HPLCESI-Q-ToF analysis enabled us to identify the triglycerides (TAGs) and diglycerides (DAGs) prole
of each resin, and FIA analysis was used as a rapid method to evaluate the presence of possible additives
such as synthetic polymers.
2013 Elsevier B.V. All rights reserved.

1. Introduction milestones in the evolution of painting techniques in the 20th cen-


tury art scene. Traditional natural binders such as proteinaceous
Alkyd resins have been diffused as commercial paint binders media and drying oils were gradually replaced by a variety of
since the 1940s, as an industrial evolution of the classical oil paint organic synthetic paint materials. Artists such as Frank Stella, Jack-
media. One of the rst alkyd paint products for artists was the son Pollock and Picasso experimented with alkyd-based paints [1].
DuLux series which DuPont began marketing in 1931. The adop- The characterization of alkyd resins in paint samples from art-
tion of these oil-based industrial polymers by artists is one of the works represents an important contribution to the study of the
painting techniques used in contemporary art. In addition, the pos-
sibility to assess the components of industrially formulated paint
Corresponding author. Tel.: +39 050 2219303; fax: +39 050 2219260. materials and to differentiate between different trademarks and
E-mail addresses: jacopo.lanasa@gmail.com (J. La Nasa), ilariad@dcci.unipi.it producers is extremely interesting, in order to solve possible attri-
(I. Degano), frances@dcci.unipi.it (F. Modugno), perla@dcci.unipi.it (M.P. Colombini). bution and dating issues, as well as to investigate decay processes

0003-2670/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.aca.2013.08.021
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 65

and interactions with other materials. Consequently, conservation coupled with mass spectrometry [1421]. Such techniques have
scientists, restorers and conservators have increasingly focused on never been applied to alkyd paint materials.
developing and evaluating analytical tools able to achieve these In this paper we describe the full characterization of com-
goals [1]. mercial alkyd paint materials using a multi-analytical approach
It has been recently demonstrated that the presence of additives based on the integration of three different mass spectrometric
in the formulation of industrial tube paints may presents a risk for techniques. We exploited gas chromatographymass spectrom-
the stability of artworks. Hydrophilic additives increase the water etry (GC/MS), high performance liquid chromatography coupled
sensitivity of paint lms, and, as a consequence, in some cases the with electrospray ionization mass spectrometry with a tandem
cleaning of modern unvarnished modern oil paintings is extremely quadrupole-time of ight mass spectrometer (HPLCESI-Q-ToF),
delicate and requires specic procedures [2]. Identifying the formu- and ow injection analysis (FIA) in the ESI-Q-ToF mass spectrome-
lation of industrial paint products for artists is thus also important ter.
for planning conservation strategies. The developed analytical approach is an useful complement to
FTIR spectroscopy, thermal analysis and analytical pyrolysis analysis by Py-GC/MS. On one hand pyrolysis achieves a qualitative
coupled with gas chromatography/mass spectrometry (Py-GC/MS) characterization of the resins and offers the possibility to identify
are the current approaches used for the chemical characterization the polyols used in the synthesis [4,6]. On the other hand, Py-GC/MS
of synthetic polymers. These techniques have been used to study cannot be performed as quantitative analysis, and in additions it
alkyd resins in paint samples and their curing processes [36]. In produces relatively complex chromatograms. Moreover, pyrolysis
particular, Py-GC/MS offers the possibility to characterize alkyd alters the molecular prole introducing thermal induced reactions
resins in short time and without any sample pretreatment. Ther- as isomerizations, loss of functional groups as hydroxyl functions,
mogravimetric analysis (TGA) has also been applied to investigate chain shortening, etc., leading to the formation of a variety of prod-
the reticulation processes of alkyds [5]. ucts not originally present in the resin. This aspect makes analytical
However, the complex chemical composition of alkyd resins pyrolysis not optimal for quantitative analysis and aging studies of
requires a multi-analytical approach for a detailed molecular anal- lipid materials. Thus, GC/MS after off line hydrolysis is a precious
ysis. complement to Py-GC/MS in the study of oxidation/degradation
Alkyds are oil-modied polyesters manufactured from poly- state of glycerolipids in general and of alkyds in particular.
ols (typically glycerol or pentaerythritol), aromatic polybasic acids We used a fully validated GC/MS method to determine the fatty
(phthalic anhydride and phthalic acids are the most common) and acid prole after a sample treatment entailing fast microwave-
a source of fatty acids, usually a vegetable oil. Drying and semi- assisted saponication. This was followed by a derivatization step
drying oils, such as linseed, soybean and castor oil are used for with BSTFA. GC/MS analysis enabled us to obtain quantitative infor-
the production of alkyd resins. Modication of alkyd paints with mation on the fatty acid content and on the presence of oxidation
additives is common in industrial production: fatty acids, acrylic, products of acylic chains. The low limits of detection and quantita-
styrene and silicone compounds, inorganic llers and driers, and tion of the method allow for identifying minimal amount of fatty
dispersing agents have been reported as possible modiers [1,7]. acids [2225]. The aromatic polybasic acids are also characterized
The fatty acid portion plays a fundamental role in regulat- by GC/MS in the same chromatographic run.
ing the properties of alkyd paints, such as cross-linking potential, HPLCESI-Q-ToF was used to determine the triglyceride prole
yellowing tendency, and compatibility with different solvents. The of the lipid fraction of alkyd paints. TAG proling enabled us to
amount and type of oil(s) used in their synthesis is extremely identify the specic oils used to produce the resins, and to gain
important in order to dene the tendency of the paint to dry and its information on the strategies used in their synthesis.
drying speed. Triglycerides, with a high content of polyunsaturated We were also able to identify individual triglycerides, thus com-
acyl chains, undergo radical-oxidative cross-linking processes and plementing the information on the fatty acid prole obtained by
are responsible for the curing of the paint lm [1,2,4,5,713]. GC/MS.
The extent of the curing and oxidation of glycerolipids can In addition, we tested the applicability of mass spectromet-
be investigated by determining their fatty acid prole by gas ric analysis by ow injection-ESI-Q-ToF. FIA-ESI-Q-ToF ngerprint
chromatography/mass spectrometry (GC/MS) after hydrolysis and enabled us to obtain the prole of the glyceride fraction and possi-
derivatization. This approach has been widely applied in the liter- ble additives in just 2 min.
ature to the characterization of traditional lipid paint binders used The integrated analytical approach was applied to three com-
in art since ancient times, such as egg yolk and drying oils. It has mercial oil-based artistic paints: Ferrario Alkyd paint containing
proved a fundamental tool for investigating painting techniques three different pigments, Winsor & Newton Grifn alkyd paint
and assessing the state of conservation of paint layers. (fast drying oil color) containing three different pigments, and
Two applications of GC/MS methods for the characteriza- Kremer alkyd resin oil (no pigment). The detailed molecular char-
tion of the fatty acid prole of alkyd resins are described acterization of these painting materials is reported. This study is
in the literature [6,7]. The rst [7] is based on hydrolysis the rst step toward the understanding of the molecular features
in presence of n-butylamine followed by derivatization with of these materials and represents the basis for future research on
N,O-bis(trimethylsilyl)triuoroacetamide (BSTFA) and hexame- aging and curing of alkyd paints in artworks.
thyldisilazane (HMDS) before the GC/MS injection. The results
suggest that GC/MS can be successfully applied to the study of the
fatty acid composition of alkyd resins, although the proposed pro-
cedure is time consuming due to the hydrolysis step (5 h for the 2. Materials and methods
hydrolysis and 30 min for the derivatization). The second method
[6] based on GC/MS reported in the literature entails a single step 2.1. Alkyd paint samples
for hydrolysis and derivatization using Meth-Prep II. The results
reported in the paper refer to qualitative analysis only, in absence Commercial artistic tubes of Ferrario Alkyd and Winsor &
of calibration curves, internal standard and method validation. Newton Grifn Fast Drying Oil Colour paints were analyzed.
An alternative approach to gain detailed information on lipid For Ferrario, three paints were considered, containing, accord-
composition is to determine the prole of the triglycerides (TAGs). ing to the supplier, the pigments iron oxide yellow (PY42), burnt
TAGs are generally proled by analytical techniques based on HPLC Sienna (PBr7) and ivory black (PBK9). The Winsor & Newton paints
66 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

contained yellow ochre (PY43), cobalt blue (PB28) and ivory black. temperature of 45 C. Separation was achieved using a gradient
All the paint tubes were purchased from Zecchi (Florence, Italy). of methanol (eluent A) and iso-propanol (eluent B). The elution
We also analyzed Kremer alkyd resin oil (pure resin, no pig- gradient was programmed as follows: 90% A for 5 min, followed
ment), directly purchased from Kremer Pigmente, GmbH & Co. by a linear gradient to 90% B in 25 min, then held for 5 min. Re-
(Aichstetten, Germany). equilibration time for each analysis was 10 min.
To test the performance of the analytical method on case- The ESI operating conditions were: drying gas (N2 , purity
studies, a paint sample (0.8 mg) was collected from the artwork >98%): 350 C and 10 L min1 ; capillary voltage 4.5 kV; nebulizer
Salto di qualit, by Patrizia Zara (Milano, Italy), 2008. According gas 35 psig; sheath gas (N2 , purity >98%): 375 C and 11 L min1 .
to the author, the artwork was painted using Winsor & Newton High resolution MS and MS/MS spectra were acquired in positive
Grifn alkyd Grifn Fast Drying Oil Colour commercial tubes. mode in the range 1001700 m/z. The fragmentor was kept at 200 V,
nozzle voltage 1000 V, skimmer 65 V, octapole RF 750 V, and the
2.2. Materials and reagents collision energy for the MS/MS experiments was set at 50 V. The
collision gas was nitrogen (purity 99.999%). The data were collected
The solvents used for the GC/MS analysis were: diethyl ether, by auto MS/MS acquisition with an MS scan rate of 1.03 spectra s1
n-hexane and isooctane (HPLC/MS grade; SigmaAldrich, U.S.A.). and an MS/MS scan rate of 1.05 spectra s1 ; only one precursor was
N,O-bis(trimethylsilyl)triuoroacetamide (BSTFA) containing 1% acquired per cycle (relative threshold 0.010%).
trimethylchlorosilane used for fatty acid derivatization was pur- The structures of individual glycerides were identied by inter-
chased from SigmaAldrich, U.S.A. preting their tandem mass spectra, where the most abundant
Fatty acid solutions were prepared in acetone, and contained fragments derive from the combined elimination of two adjacent
lauric acid (4.10 g g1 ), suberic acid (4.27 g g1 ), azelaic acid fatty acid residues. Structural assignation was based on the assump-
(3.95 g g1 ), myristic acid (4.11 g g1 ), sebacic acid (3.85 g g1 ), tion, made on the basis of literature data, that the formation of
palmitic acid (4.39 g g1 ), linolenic acid (6.50 g g1 ), linoleic acid sn-1 and sn-3 diacylglycerol ions in the tandem mass spectra is
(5.20 g g1 ), oleic acid (6.32 g g1 ), stearic acid (6.62 g g1 ), energetically more favored than the loss of the acyl chain in sn-2
and ricinoleic acid (5.47 g g1 ). All standard solutions were used position [11,18,2628]. Fragmentation patterns for the identied
to derive calibration curves. The acids were purchased from triglycerides are reported in Table 1. The following abbreviations
SigmaAldrich, U.S.A. (purity >99%). were used to indicate acyl substituents in TAGs and DAGs: Rn: rici-
Tridecanoic acid (purity 99%; SigmaAldrich, U.S.A.) solution noleyl (C18:1,OH ); Ln: linolenyl (C18:3 ); L: linoleyl (C18:2 ); O: oleyl
in isooctane, 139.91 g g1 , was used as an internal standard for (C18:1 ); S: stearyl (C18:0 ); Po: palmitoleyl (C16:1 ); P: palmityl (C16:0 );
derivatization; hexadecane (purity 99%; SigmaAldrich, U.S.A.), U: undecyl (C11:0 ).
solution in isooctane, 142.00 g g1 , was used as an internal The mass axis was calibrated using the Agilent tuning mix
standard for injection. HP0321 (Agilent Technologies U.S.A.) prepared in acetonitrile and
The solvents used for the HPLC and FIA analysis were: iso- was also corrected online by tuning with the m/z 121.0509 and
propanol, n-hexane and methanol (HPLC/MS grade; Fluka, U.S.A.). 922.0098 from a reference solution in acetonitrile/water of purine
and HP0921 reference solution (Agilent Technologies, U.S.A.).
2.3. Instruments and methods MassHunter Workstation Software (B.04.00) was used to carry
out mass spectrometer control, data acquisition, and data analysis
2.3.1. Gas chromatography/mass spectrometry [21].
GC/MS instrumentation consisted of a Trace GC 2000 chromato-
graphic system equipped with a PTV injection port and coupled to 2.3.3. Flow injection analysis
an ITQ 900 ion trap (Thermo Quest, U.S.A.). The applicability of FIA-ESI-Q-ToF was tested as a fast nger-
Samples were injected in splitless mode at 280 C. GC sep- printing technique, in order to evaluate its capacity to obtain
aration was performed on a fused silica capillary column information on the TAG proles directly in hexane extracts without
HP-5MS (J&W Scientic, Agilent Technologies, US, stationary phase chromatographic separation.
5% diphenyl95% dimethyl-polysiloxane, 30 m length, 0.25 mm FIA-ESI-Q-ToF ow injection analysis (FIA) was carried out using
i.d., 0.25 m lm thickness). Chromatographic conditions were a 1200 Innity HPLC coupled to a Jet Stream ESI interface with a
adapted from [22,23]: initial temperature 80 C, 2 min isothermal, Quadrupole-Time of Flight tandem mass spectrometer 6530 Inn-
10 C min1 up to 200 C, 4 min isothermal for the separation of ity Q-TOF (Agilent Technologies, U.S.A.).
unsaturated C18 fatty acids and their isomers, 6 C min1 up to The eluents were methanol and iso-propanol (90:10); the ow
280 C, 40 min isothermal. The helium (purity 99.9995%) gas ow rate was 0.2 mL min1 and the injection volume was1 L.
was set in constant ow mode at 1.2 mL min1 . MS parameters: The ESI and MS operating conditions were the same as for the
electron impact ionization (EI, 70 eV) in positive mode; ion source HPLC [21,29].
temperature 230 C; scan range 50700 m/z; interface temperature
280 C. The injection volume was 2 L. 2.4. Sample treatment
Peak assignment was based on a comparison with library mass
spectra (NIST 1.7, WILEY275). The analytical procedure for characterizing the paint materi-
als is reported in Fig. 1. In detail, 35 mg of each fresh resin were
2.3.2. High performance liquid chromatography/mass submitted to extraction in an ultrasonic bath at 60 C with hexane
spectrometry (600 L) for 5 min. Then,
HPLCESI-Q-ToF analyses were carried out using a 1200 Innity
HPLC, coupled with a Quadrupole-Time of Flight tandem mass spec- For the GC/MS analysis an analytical procedure successfully
trometer 6530 Innity Q-ToF detector by a Jet Stream ESI interface applied for the characterization of drying oil was used [2225]:
(Agilent Technologies, U.S.A.). 200 L of the extract were subjected to saponication assisted
The HPLC conditions were: Poroshell 120 EC-C18 column by Milestone (U.S.A.) microwaves Ethos One (power 200 W)
(3.0 mm 50 mm, 2.7 m particle size) with a Zorbax eclipse plus with 300 L of KOHETOH 10% wt at 80 C for 60 min. In order
C-18 guard column (4.6 mm 12.5 mm, 5 m particle size); a ow to maximize the extraction yield, two solvents were used:
rate of 0.3 mL min1 , an injection volume of 1 L and a column the neutral compounds were extracted with n-hexane; the
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 67

Table 1
Observed DAGs and TAGs in the HPLCESI-Q-ToF chromatograms of the alkyd resins. Acyl substituent abbreviations: Rn: ricinoleyl (C18:1,OH ); Ln: linolenyl (C18:3 ); L: linoleyl
(C18:2 ); O: oleyl (C18:1 ); S: stearyl (C18:0 ); Po: palmitoleyl (C16:1 ); P: palmityl (C16:0 ); U: undecyl (C11:0 ).

DAG/TAG MS1 MS2

Assigned structure Precursor ion Formula Daughter ions

657.4506 [M+Na]+
+ 337.2701 [MC18 H33 O3 ]+
RnL 657.4506 [C39 H70 O6 +Na]
377.2615 [MC18 H39 O4 +Na]+
321.2365 [C18 H33 O3 ]+

637.4779 [M+Na]+
LnL 637.4779 [C39 H66 O5 +Na]+ 337.2560 [MC18 H29 O2 ]+
335.2560 [MC18 H31 O2 ]+

639.5032 [M+Na]+
LL 639.5032 [C39 H68 O5 +Na]+ 337.2701 [MC18 H31 O2 ]+
303.2146 [C18 H31 O2 ]+

641.5123 [M+Na]+
LO 641.5123 [C39 H70 O5 +Na]+ 339.2827 [MC18 H31 O2 ]+
337.2670 [MC18 H33 O2 ]+

823.6515 [M+Na]+
+ 639.4877 [MC11 H21 O2 +Na]+
ULnRn 823.6515 [C50 H88 O7 +Na]
525.3947 [MC18 H33 O3 ]+
541.3793 [MC18 H29 O2 +Na]+

919.8047 [M+Na]+
639.4935 [MC18 H31 O2 +Na]+
RnLL 919.8047 [C57 H100 O7 +Na]+ 621.4813 [MC18 H33 O3 +Na]+
599.4984 [MC18 H33 O3 ]+
321.2374 [C18 H33 O3 +Na]+

921.8008 [M+Na]+
643.5197 [MC18 H31 O2 +Na]+
RnLO 921.8008 [C57 H102 O7 +Na]+ 641.5023 [MC18 H33 O2 +Na]+
623.5112 [MC18 H33 O3 +Na]+
321.2362 [C18 H33 O3 +Na]+

923.8025 [M+Na]+
643.5197 [MC18 H31 O2 +Na]+
RnLS 923.8025 [C57 H104 O7 +Na]+ 641.5094 [MC18 H35 O2 +Na]+
603.5273 [MC18 H33 O3 ]+
321.2365 [C18 H33 O3 +Na]+

805.6313 [M+Na]+
621.4784 [MC11 H21 O2 +Na]+
ULnLn 805.6313 [C50 H88 O6 +Na]+ 599.5118 [MC11 H21 O2 ]+
525.3947 [MC18 H29 O2 +Na]+
503.4111 [MC18 H29 O2 ]+

895.6777 [M+Na]+
617.4496 [MC18 H29 O2 +Na]+
LnLnLn 895.6777 [C57 H92 O6 +Na]+
595.4673 [MC18 H29 O2 ]+
301.2104 [C18 H29 O2 ]+

897.6922 [M+Na]+
619.4641 [MC18 H29 O2 +Na]+
LLnLn 897.6922 [C57 H94 O6 +Na]+ 617.4487 [MC18 H31 O2 +Na]+
597.4823 [MC18 H29 O2 ]+
595.4663 [MC18 H31 O2 ]+

873.6940 [M+Na]+
+ 617.4607 [MC16 H31 O2 +Na]+
LnLnP 873.6940 [C55 H94 O6 +Na]
595.4775 [MC16 H31 O2 ]+
573.4937 [MC18 H29 O2 +Na]+

899.7129 [M+Na]+
621.4910 [MC18 H29 O2 +Na]+
LnLL 899.7129 [C57 H96 O6 +Na]+ 617,4479 [MC18 H31 O2 +Na]+
599.4974 [MC18 H29 O2 ]+
597.4661 [MC18 H31 O2 ]+

901.7281 [M+Na]+
LLL 901.7281 [C57 H98 O6 +Na]+ 621.4826 [MC18 H31 O2 +Na]+
599.4881 [MC18 H31 O2 ]+

877.7246 [M+Na]+
621.4775 [MC16 H31 O2 +Na]+
PLL 877.7246 [C55 H98 O6 +Na]+
599.4776 [MC16 H31 O2 ]+
575.4961 [MC18 H31 O2 ]+
68 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

Table 1 (Continued)

DAG/TAG MS1 MS2

Assigned structure Precursor ion Formula Daughter ions

903.7451 [M+Na]+
623.4954 [MC18 H31 O2 +Na]+
LLO 903.7451 [C57 H100 O6 +Na]+ 621.4798 [MC18 H33 O2 +Na]+
601.5169 [MC18 H31 O2 ]+
599.4986 [MC18 H33 O2 ]+

879.7449 [M+Na]+
623.4957 [MC16 H31 O2 +Na]+
601.5116 [MC16 H31 O2 ]+
LOP 879.7449 [C55 H100 O6 +Na]+ 599.4796 [MC18 H31 O2 +Na]+
597.4796 [MC18 H33 O2 +Na]+
577.5127 [MC18 H31 O2 ]+
575.4982 [MC18 H33 O2 ]+

905.7613 [M+Na]+
625.5103 [MC18 H31 O2 +Na]+
LLS 905.7613 [C57 H102 O6 +Na]+ 621.4778 [MC18 H35 O2 +Na]+
603.5286 [MC18 H31 O2 ]+
599.4967 [MC18 H35 O2 ]+

881.7548 [M+Na]+
621.4981 [MC16 H31 O2 +Na]+
OOP 881.7548 [C55 H98 O6 +Na]+ 597.4981 [MC18 H31 O2 +Na]+
599.4856 [MC16 H31 O2 ]+
575.5157 [MC18 H31 O2 ]+

907.7764 [M+Na]+
627.5499 [MC18 H31 O2 +Na]+
625.5229 [MC18 H33 O2 +Na]+
OLS 907.7764 [C57 H104 O6 +Na]+ 623.5070 [MC18 H35 O2 +Na]+
605.5520 [MC18 H31 O2 ]+
603.5404 [MC18 H33 O2 ]+
601.5239 [MC18 H35 O2 ]+

1182.0142 [M+Na]+
901.7192 [MC18 H29 O2 +Na]+
ORnLL 1182.0142 [C74 H130 O8 +Na]+ 621.4788 [C39 H67 O4 +Na]+
599.4965 [C39 H67 O4 ]+
583.4646 [C36 H65 O4 +Na]+

1184.0146 [M+Na]+
903.7318 [MC18 H31 O2 +Na]+
ORnLO 1184.0146 [C74 H132 O8 +Na]+ 623.4787 [C39 H69 O4 +Na]+
601.5113 [C39 H69 O4 ]+
583.4634 [C36 H65 O4 +Na]+

1186.0187 [M+Na]+
905.7456 [MC18 H33 O2 +Na]+
ORnLS 1186.0187 [C74 H134 O8 +Na]+ 625.5081 [C39 H71 O4 +Na]+
603.5265 [C39 H71 O4 ]+
583.4626 [C36 H65 O4 +Na]+

1463.3857 [M+Na]+
1184.9003 [MC18 H29 O2 +Na]+
1182.9558 [MC18 H33 O2 +Na]+
901.7217 [C57 H99 O6 +Na]+
ORnRnLL 1463.3857 [C93 H168 O10 +Na]+
864.7070 [C54 H97 O6 +Na]+
621.4818 [C39 H67 O4 +Na]+
599.5001 [C39 H67 O4 ]+
583.4669 [C36 H65 O4 +Na]+

residual solution was acidied with hydrochloric acid (6 M) For the FIA analysis, 200 L of the extract were dried under a
and then carboxylic acids were extracted with diethyl ether nitrogen stream, diluted with the elution mixture and ltered on
(200 L, three times). The two extracts (neutral + acid fraction) a 0.45 m PTFE lter (Grace Davison Discovery Sciences, U.S.A.)
were combined for GC/MS analysis in order to analyze them just before injection.
in a single chromatographic run evaporated to dryness under
nitrogen stream and subjected to derivatization with 20 L of 2.5. Quantitative analysis
N,O-bistrimethylsilyltriuoroacetamide (BSTFA), 200 L of isooc-
tane and 5 L of tridecanoic acid solution at 60 C for 30 min. 5 L A GC/MS quantitative analysis was performed using calibration
of hexadecane solution were added just before injection. curves calculated on the basis of the extract ion chromatograms
For the HPLCMS analysis, 200 L of the extract were puried (extracted m/z: lauric acid 117257, suberic acid 169303, azelaic
with a water/ethanol 1:2 mixture (50 L) three times (adapted acid 149317, myristic acid 117285, sebaci acid 149331, palmtic
from [20]), dried under a nitrogen stream, diluted with the elu- acid 1173131, linolenic acid 117335, linoleic acid 117337, oleic
tion mixture and ltered on a 0.45 m PTFE lter (Grace Davison acid 117339, stearic acid 117341, ricinoleic acid 187328). The
Discovery Sciences, U.S.A.) just before injection. quantitative analysis of undecanoic acid was performed on the basis
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 69

Sample (3-5 mg)

Hexane extraction
(600 L)

GC/MS analysis HPLC-ESI-Q-ToF analysis FIA-ESI-Q-ToF analysis

Saponification assisted Purification with Dried under N 2


with microwave ethanol/water mixture
(2:1)
Diluted with
Extraction with hexane methanol/iso-propanol
Dried under N2 (90:10)

Acidification with HCl


Diluted with Synthetic polymers used as additives
methanol/iso-propanol
Extraction with diethyl (90:10)
ether

Derivatization with Glyceride profile


BSTFA High molecular weight synthesis products

Fatty acid profil e


Neutral fraction
Aromatic fraction
Additives

Fig. 1. Analytical procedure for the characterization of alkyd resins.

Table 2
Fatty acid proles (%) of the Ferrario, Winsor & Newton and Kremer alkyd resins based on GC/MS. The proles of the reference material are compared to the one of the Patrizia
Zara paint sample from the artwork Salto di Qualit (2008). The relative standard deviation (RSD%) for all the fatty acids was lower than 3%.

Compounds Lipid fraction (% of individual fatty acids) Paint sample (2008)

Ferrario Winsor & Newton Kremer

Undecanoic acid 4a
Azelaic acid 35
Sebacic acid 4
Palmitic acid 18 13 7 22
Linolenic acid 8
Linoleic acid 53 28 58 1
Oleic acid 21 26 10 3
Stearic acid 8 8 7 16
Ricinoleic acid 16 14 19
a
Calculated on the basis of the lauric acid calibration curves.

of lauric acid calibration curves. Replicate analyses were performed The results of GC/MS analysis are reported in Tables 2 and 3.
to ensure the reliability of the data presented. The relative abundances of the identied TAG and DAG species are
For the HPLCESI-Q-ToF quantitation, relative abundances were reported in Table 4. The DAG and TAG distributions are reported as
calculated on the basis of extract ion chromatograms, considering normalized histograms in Fig. 2.
the isotopic distribution of the molecular species, and normalized The results highlight important differences in the formulation
to 100%. of the three sets of materials.

3. Results and discussion 3.1. Ferrario alkyd resin

This section reports and discusses the results obtained by The GC/MS total ion chromatogram of a Ferrario paint is
GC/MS, HPLCESI-Q-ToF and FIA-ESI-Q-ToF techniques for the anal- reported in Fig. 3. The fatty acid prole of Ferrario resin is char-
ysis of Winsor & Newton, Ferrario and Kremer paint samples. acterized by the presence of palmitic, stearic, oleic (cis and trans

Table 3
Molecular markers identied in the aromatic fraction of the Ferrario, Winsor & Newton and Kremer alkyd resins by GC/MS analysis. The characteristics of the reference
materials are compared to the ones of the Patrizia Zara paint sample from the artwork Salto di Qualit (2008).

Compounds Aromatic fraction Paint sample (2008)

Ferrario Winsor & Newton Kremer



1,2-Benzendicarboxylic acid

1,3-Benzendicarboxylic acid
70 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

Table 4
Ferrario
TAG s and DAGs proles (%) of the Ferrario, Winsor & Newton and Kremer alkyd
resins acquired by HPLCESI-Q-ToF. Acyl substituent abbreviations: Rn: ricinoleyl 100

Relative abundance [%]


(C18:1,OH ); Ln: linolenyl (C18:3 ); L: linoleyl (C18:2 ); O: oleyl (C18:1 ); S: stearyl (C18:0 );
Po: palmitoleyl (C16:1 ); P: palmityl (C16:0 ); U: undecyl (C11:0 ). 80

DAG/TAG Relative abundances (%) Paint sample 60


(2008)
Ferrario Winsor & Newton Kremer
40
RnL 1.4
LnL 0.9 20
LL 1.0 0.6 1.5
LO 1.1 0.9 1.0 0

RnLO

LLO

ORnRnLL
ORnLS
RnLL

ORnLO
RnLS

OOP
LO

ORnLL
LOP

OLS
RnL

LL

ULnRn
LnL

LLL
ULnLn

LLnLn

PLL

LLS
LnLL
LnLnLn

LnLnP
ULnRn 0.6
RnLL 8.6
RnLO 4.2
RnLS 5.4
ULnLn 5.2
LnLnLn 8.5 18.7 21.9
LLnLn 8.8 14.5 16.5 Winsor & Newton
LnLnP 2.7 2.7 100

Relative abundance [%]


LnLL 13.3 21.6 22.1
LLL 14.5 7.1 33.7 6.9 80
PLL 9.2 1.6 1.6
LLO 19.8 18.8 6.6 17.5 60
LOP 8.0 2.7 4.1
LLS 8.3 6.6 4.4 3.6 40
OOP 6.3 1.7 1.4
OLS 1.1 1.6 1.7 20
ORnLL 11.9
ORnLO 3.4 0

RnLO

ORnRnLL
ORnLS
RnLL

ORnLO
OOP
LLO

ORnLL
LOP

OLS
RnL
LnL

LLL
ULnLn
ORnLS 5.7

RnLS

LLnLn

PLL

LLS
LO
LL

ULnRn

LnLL
LnLnP
LnLnLn
ORnRnLL 6.4

isomers), and linoleic acids (Tables 2 and 3). The aromatic compo- Kremer
nent is represented by 1,3-benzendicarboxylic acid. The fatty acid 100
Relative abundance [%]

fraction reveals that the chemical compositions of the three tubes


80
were the same independently from the pigment: the observed dif-
ferences are in the range of variability of the method. 60
The HPLC chromatogram of Ferrario alkyd extract is reported in
40
Fig. 4. The rst portion of the chromatogram is characterized by
the presence of diglycerides, such as LL (m/z 639.5032, [M+Na]+ ), 20
and LO (m/z 641.5123, [M+Na]+ ). The second portion of the chro-
matogram is characterized by the presence of TAGs. Linolenyl, 0
RnLO

ORnRnLL
ORnLS
RnLL

ORnLO
OOP
LLO
LOP

OLS
RnL
LnL

LLL
RnLS

LLnLn

PLL

LLS
LO

ORnLL
LL

ULnRn

ULnLn

LnLL
LnLnP
LnLnLn

linoleyl and oleyl are the main acyl substituents. As expected


from the literature, the elution order follows the equivalent car-
bon number (dened by the formula: ECN = CN 2n, where E is
equivalent, CN is the acyl carbon number and n is the number Fig. 2. TAGs distribution in the alkyd resins.
of double bonds [14]): LnLnLn (m/z 895.6777, [M+Na]+ ), LnLnL
(m/z 897.6922, [M+Na]+ ), LnLL (m/z 899.7129, [M+Na]+ ), LLL (m/z
901.7281, [M+Na]+ ) and LLO (m/z 903.7451, [M+Na]+ ) elute in this
order. At higher retention times, TAGs containing saturated sub- [M+Na]+ ), m/z 879.7250 (LOP, [M+Na]+ ) and m/z 881.7150 (OOP,
stituents elute. The main TAGs in this group are LLP (m/z 877.7246, [M+Na]+ ). The main ions in the second cluster are: m/z 901.7223
[M+Na]+ ), LOP (m/z 897.7449, [M+Na]+ ) and LLS (m/z 905.7613, (LLL, [M+Na]+ ), m/z 903.7361 (LLO, [M+Na]+ ) and m/z 905.7412 (LLS,
[M+Na]+ ). HPLC analysis highlighted the presence of conforma- [M+Na]+ ). Mass peaks with the lowest intensities are attributed to
tional isomers of unsaturated fatty acids, most probably formed due LnLnLn (m/z 895.6777, [M+Na]+ ), LnLnL (m/z 897.7159, [M+Na]+ )
to the high temperature conditions applied to achieve transesteri- and LnLL (m/z 899.7159, [M+Na]+ ).
cation during the synthesis of the commercial product [30,31]. This At higher m/z values, ion clusters due to the polymer deriving
result is consistent with the detection of both cis and trans isomers from the transesterication process used for the synthesis were
of octadecadienoic acid (oleic acid) by GC/MS. observed [34]. The ow injection analysis shows the absence of
With regard to the FIA-ESI-Q-ToF analysis, the ngerprint mass residual free polyols and polybasic acids.
spectrum of Ferrario alkyd resin (Fig. 5a) is dominated by the Comparing the triglyceride prole observed for this resin to
presence of a Gaussian distribution of peaks around m/z 555.4218 a set of reference oils, similarities with linseed oil and soy-
characterized by a m/z of 44 units. This prole can be attributed bean are observed [21]. These two plant oils are characterized
to polyethylene glycol, a known additive used in the production by a similar composition, and by the presence of consistent
of alkyd resins: since the main polyethylene glycols ion cluster is amounts of triglycerides containing linolenyl and linoleyl acyl sub-
characterized by a double charge ([M]2+ ), the prole of the polymer stituents. The relative abundances of the triglycerides in Ferrario
is compatible with the one of PEG2000 [32,33]. The TAG fraction is resin, and the presence of both LLO, characteristic of soybean
visible in the range 800 and 910 m/z (Fig. 5b). The observed trigly- oil, and of LnLnLn, characteristic of linseed oil, suggest that the
cerides can be subdivided into two different clusters on the basis of alkyd resins was produced from a mixture of these two raw
their m/z: in the rst cluster, the main m/z are: m/z 877.7205 (LLP, materials [21].
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 71

1,3-benzenedicarboxylic acid
100

linoleic acid
oleic acid (cis)
oleic acid (trans)
Relave abundance (%)

palmic acid

stearic acid
IS2
IS1

12 14 16 18 20 22 24 26
Time (min)

Fig. 3. GC/MS chromatogram of the extract of Ferrario Alkyd paint (PY42); IS1: hexadecane, IS2: tridecanoic acid.

The results of HPLC and FIA analysis of paint containing different and ricinoleic acids (Tables 2 and 3). The three selected Winsor
pigments do not show signicant differences. & Newton paint tubes show the same fatty acid composition. The
aromatic fraction was made up of 1,2-benzendicarboxilyc and 1,3-
3.2. Winsor & Newton benzendicarboxilyc acids: our procedure allowed us to characterize
two different phthalic acid isomers, not detected in previous stud-
The GC/MS chromatogram of a sample of Winsor & Newton ies performed by GC/MS [6,7]. Ricinoleic acid is considered in the
paint is reported in Fig. 6. GC/MS analysis highlighted that the literature as a molecular marker of castor oil, while linolenic acid is
hydrolyzed fraction of Winsor & Newton alkyd resin contains indicative of linseed or soybean oil. The presence of conformational
palmitic, stearic, oleic (cis and trans isomers), linoleic, linolenic isomers of unsaturated fatty acids is related to heating processes
LLO
LLL

LLS
LOP
LLP
LnLL

OOP
LnLnLn

OLS
LnLnL
LO
*
LL

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
Counts vs. Acquisition Time (min)

Fig. 4. HPLC-ESI-Q-ToF chromatogram of the extract of the Ferrario Alkyd paint (PY42); the gure was obtained by overlapping the extract ion chromatograms relative to
the 12 identied TAG species; (*) contamination.
72 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

Fig. 5. FIA-ESI-Q-ToF high resolution mass spectrum of Ferrario alkyd resin (PY42) (a) and zoom of the mass range m/z 870920 (b).
linoleic acid

100
oleic acid (cis)
oleic acid (trans)
1,2-benzenedicarboxylic acid

1,3-benzenedicarboxylic acid
Relave abundance (%)

ricinoleic acid
palmic acid

stearic acid
linolenic acid
IS2
IS1

12 14 16 18 20 22 24 26 28
Time (min)

Fig. 6. GC/MS chromatogram of the extract of Winsor & Newton Grifn Fast Drying Oil Colour (PY43); IS1: hexadecane, IS2: tridecanoic acid; (*) contamination.
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 73

LnLL

LLO
LnLnLn
LnLnL

LLL

LLS
LLP
LnLnP

LOP

OLS
OOP
ox TAG 1

ox TAG 2
LL
LO
LLn

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
Counts vs . Acquisi tion Time (min)

Fig. 7. HPLC-ESI-Q-ToF chromatogram of the extract of Winsor & Newton Grifn Fast Drying Oil Colour (PY43); the gure was obtained by overlapping the extract ion
chromatograms of 14 identied TAG species.

Fig. 8. Tandem mass spectra and fragmentation pattern of oxidized TAGs characterized by m/z 961.7948 and 945.807.
74 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

5
x10

2.8 899.7103
2.6

2.4

2.2 945.8091
2

1.8

1.6

1.4

1.2

1 961.7964
0.8 155.1215
0.6 639.4963
285.1663 417.3533
0.4 1123.8204
801.5378 1388.0454
0.2

0
200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900
Counts vs. Mass-to-Charge (m/z)

Fig. 9. FIA-ESI-Q-ToF high resolution mass spectrum of Winsor & Newton alkyd paint (PY43).

applied during the synthesis [35], as mentioned for the Ferrario [3,15,37]. The absence of ions due to free ricinoleic acid (and free
resin. fatty acids in general) in the ow injection mass spectrum is due to
The HPLC chromatogram of the Winsor & Newton Grifn alkyd the low ionization yield of this acid in the experimental conditions
resin is shown in Fig. 7. The TAG prole of this resin is very similar adopted for TAGs and DAGs analysis.
to the one observed for the Ferrario resin, except for the presence Comparing the obtained triglyceride prole of Winsor & Newton
of oxidized TAGs (Fig. 8) at short retention times. As expected, the alkyd paint to a database of reference oils, the lipid ingredient used
rst part of the chromatogram is characterized by DAGs followed in the preparation of the paint material appears to be a mixture
by the TAG fraction. The TAG distribution (Fig. 2) of this resin dif- of linseed and soybean oil, on the basis of the same considerations
fers from the Ferrario distribution in terms of the higher relative made for Ferrario resin [21].
abundance of TAGs containing linolenic acid. Although GC/MS anal- The three selected Winsor & Newton alkyd paints containing
ysis highlighted the presence of ricinoleic acid, it is notable that different pigments show the same qualitative and quantitative
glycerides containing ricinoleyl units are absent in the HPLCMS chemical composition.
chromatogram.
The FIA-MS ngerprint mass spectrum of the Winsor & New- 3.3. Kremer alkyd resin oil
ton alkyd resin (Fig. 9) shows the presence of the DAG and TAG
fractions. The ions m/z 637.4912 (LnL, [M+Na]+ ), m/z 639.4856 (LL, The fatty acid prole of the Kremer alkyd resin oil after saponi-
[M+Na]+ ) and m/z 641.5004 (LO, [M+Na]+ ) are characteristic of DAG cation is reported in Table 2 and the total ion chromatogram in
fractions. The composition of the TAG fraction is very similar to the Fig. 10. It is characterized by palmitic, stearic, oleic (cis and trans
one of the Ferrario resin, except for two intense ions (945.8091 and isomers), linoleic (Z,Z, Z,E and E,E isomers), ricinoleic (cis and trans
961.7964), characteristic of the oxidized TAGs In the FIA-ESI mass isomers), and undecanoic acids. The amount of linoleic acid (58%)
spectrum. is particularly high in the GC/MS chromatogram compared to the
In agreement with the HPLC results, no ions at m/z correspond- other materials and to the values reported in the literature for the
ing to glycerides containing the ricinoleyl group were identied. majority of plant oils. GC/MS analysis highlighted the absence of
As observed for the Ferrario, ion clusters due to the polymer deriv- aromatic compounds, indicating that this material is not a conven-
ing from the transesterication process used for the synthesis are tional alkyd resin.
observed at higher m/z values [34]. The high relative abundance of The HPLCMS prole of the Kremer alkyd resin oil is reported in
the triglyceride fraction suggests that the main component of the Fig. 11. The DAGs RnL (m/z 657.4506, [M+Na]+ ), LL (m/z 639.5032,
commercial product is the drying oil. No free polyols and polybasic [M+Na]+ ) and LO (m/z 641.5123, [M+Na]+ ) are shown in the rst
acids are identied. portion of the chromatogram. The second portion highlights the
Flow injection analysis shows the absence of additives, such predominance of TAGs with a ricinoleyl unit as an acyl sub-
as polyethylene glycol identied in the Ferrario resins, and the stituent, characteristic markers of castor oil: RnLL (m/z 919.8047,
presence of the ion m/z 110.0490 that can be due to presence of [M+Na]+ ), RnLO (m/z 921.8008, [M+Na]+ ) and RnLS (m/z 923.8025,
2-butanone oxime, used as anti-skinning additive in the resin for- [M+Na]+ ). At higher retention times, 12-acyltriglycerides and 12-
mulation [36]. 12 -acyltriglycerides (triglyceride estolides) were detected: ORnLL
The glyceride prole derived both from the HPLC chromatogram (m/z 1182.0142, [M+Na]+ ), ORnLO (m/z 1184.0146, [M+Na]+ ),
and the FIA mass spectrum shows the absence of DAGs and TAGs ORnLS (m/z 1186.0187, [M+Na]+ ) and ORnRnLL (m/z 1463.3857,
including a ricinoleyl unit. In absence of ricinoleyl-triglycerides, the [M+Na]+ ). The spectrum of ORnRnLL is reported and interpreted
identication of ricinoleic acid in the GC/MS analysis suggests that in Fig. 12. The presence of ricinoleic acid in the GC/MS fraction sug-
this fatty acid was mixed as an additive. The purpose of this for- gests the use of castor oil in the preparation of the resin and is
mulation could be to improve the siccative proprieties of the resin: clearly conrmed by the detection of specic TAGs, including the
the drying speed depends on the amount of unsaturated fatty acids ricinoleyl chain, in the HPLC chromatogram.
incorporated in the alkyd resin. The use of ricinoleic acid for this The absence of triricinolein (RnRnRn, m/z 955.7587, [M+Na]+ ),
purpose is reported in the literature and in a patented formulation which is usually very abundant in raw castor oil, and the high
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 75

Fig. 10. GC/MS chromatogram of the extract of Kremer alkyd resin oil; IS1: hexadecane, IS2: tridecanoic acid; (*) contamination.

abundance of LLL can be explained by the strong heating treatment also explains the occurrence of different conformational isomers
used for increasing the siccative proprieties of the resin through of different TAGs. In addition ULnRn (m/z 823.6515, [M+Na]+ ) and
dehydration involving the free hydroxyl groups of ricinoleyl sub- ULnLn (m/z 805.6313, [M+Na]+ ), triglycerides containing unde-
stituents. These types of reactions take place at a high temperature, canoic acid, are present in the TAG prole of Kremer alkyd resin oil.
around 150260 C [34,35], depending on the type of catalyst; The TAGs containing this acyl substituent have never been observed in
heating process also caused the transestericationcondensation a natural oil, and thus can only be formed in the above-mentioned
reactions involving the hydroxyl group of Rn chains, leading to the transesterication process after the addition of undecanoic acid
formation of 12-acyltriglycerides and 12-12 -acyltriglycerides, and in the reaction mixture. Undecanoic acid has been reported as an
DAGs such as RnL, LL and LO as secondary products [3,9]. Heating antifungal additive [38].
LLL
RnLS + RnLO (conformational isomer)

RnLO (conformational isomer)

LLO

ORnLL
RnLO

ORnRnLL
LL

ORnLS
ORnLO
RnL

LLS
ULL
LO
ULnRn

2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
Counts vs . Acquisition Time (min)

Fig. 11. HPLC-ESI-Q-ToF chromatogram of extract of the Kremer alkyd resin oil; the gure was obtained by overlapping the extract ion chromatograms relative to the 14
identied TAG species.
76 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

Fig. 12. Tandem mass spectrum and fragmentation pattern of ORnRnLL sodiate adduct.

The ESI-Q-ToF ngerprint mass spectrum of the Kremer alkyd of the ion clusters characteristic of the alkyd resin polymer,
oil, shown in Fig. 13, appears less complex than those of the conrming the oil-nature of the resin.
Ferrario and Winsor & Newton resins. FIA analysis conrmed Summarizing, the GC/MS prole of Kremer alkyd oil high-
the presence of the TAGs, DAGs, 12-acyltriglycerides and 12-12 - lighted the presence of oleic, linoleic and ricinoleic acids, which
acyltriglycerides identied by HPLC. The ions at m/z 639.4963 (LL, are molecular markers of castor oil, and undecanoic acid. No aro-
[M+Na]+ ) and m/z 657.5071 (RnL, [M+Na]+ ) are specic of DAG matic fraction was identied. The high amount of linoleic acid
fractions. The peaks at m/z 805.6313 and m/z 823.6515 are due in the GC/MS chromatogram, and of linoleyl-containing triglyce-
to ULnLn, [M+Na]+ and ULnRn, [M+Na]+ , respectively. The main rides, in the HPLC chromatogram suggest that the material was
triglyceride ion cluster is centered at m/z 901.7360 (LLL, [M+Na]+ ) dehydrated and transesteried at high temperatures. HPLCMS
and m/z 919.7258 (RnLL, [M+Na]+ ). The two clusters centered on analysis showed the presence of DAGs, 12-acyltriglycerides and
the ions m/z 1182.0142 and m/z 1463.2083 correspond to the four 12-12 -acyltriglycerides not present in castor oil. These products
and ve acyl chain glycerides deriving from castor oil through derive from transesterication reactions involving the hydroxyl
the above-mentioned dehydratationtransesterication process. group of ricinoleyl chains. In conclusion, this paint material
In contrast to the Ferrario and Winsor & Newton resins, the mass is not an alkyd paint, but an industrially modied oil con-
spectrum acquired by ow injection analysis shows the absence taining castor oil as its main component. The modications

6
x10
1.5
1.45
1.4
1.35
919.7360
1.3
1.25
901.7258
1.2
1.15
1.1
1.05
1182.0142
1
0.95
0.9
0.85
0.8 1199.9748
0.75
0.7
0.65
0.6
0.55
0.5
0.45 937.7483 1463.2083
0.4
0.35 657.5071
0.3
0.25 639.4963
823.6515
0.2
1085.8694
0.15 805.6313
0.1
0.05
0
250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600 1650
Counts vs . Mass -to-Charge (m/z)

Fig. 13. FIA-ESI-Q-ToF high resolution mass spectrum of Kremer alkyd resin.
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 77

100

1,2-benzenedicarboxylic acid
4-hydroxyhex-2-enoic acid
IS1
Relave abundance (%)

IS2

azelaic acid

2-hydroxyazelaic acid
1,3-benzenedicarboxylic acid

ricinoleic acid
linoleic acid oleic acid
sebacic acid

stearic acid
3-methyl-hexanedioic acid

palmitic acid

Hydroxy acids
0
12 14 16 18 20 22 24 26
Time (min)

Fig. 14. GC/MS chromatogram of the extract of the paint sample collected from Salto di Qualit (Patrizia Zara, 2008); IS1: hexadecane, IS2: tridecanoic acid; (*) contamination.

included a combination of transesterication and dehydration, 4. Analysis of a paint sample


which leads to a paint with high siccative proprieties. The
presence of TAGs containing undecanoic acid, which are not The proposed analytical methods have been applied to a paint
present in nature, suggest that this acid was added during the sample from an artwork, in order to evaluate the performances of
synthesis. this approach on a case study. The sample (0.8 mg) was collected
ox TAG 2
ox TAG 1

ox TAG ( [M+Na]+=929.8174)
ox TAG ( [M+Na]+=917.7689)
ox TAG ( [M+Na]+=959.7837)

[M+Na]+=943.7893)

LnLnL
LnLnLn

LnLL
ox TAG (

LLO
LLL
LLP

LLS
LOP

OLS

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
Counts vs . Acquisition Time (min)

Fig. 15. HPLCESI-Q-ToF chromatogram of the extract of the paint sample Salto di Qualit (Patrizia Zara, 2008): the chromatogram was obtained by overlapping the extract
ion chromatograms of the 15 identied TAG species.
78 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

x10 5 191.0894
1.8
a
1.7

1.6
945.8293
1.5

1.4

1.3

1.2

1.1

0.9

0.8 929.8361

0.7

0.6 397.2953

0.5
961.8058
0.4
285.1691
0.3 465.1743
827.7086
0.2 687.2434

0.1 1135.2864

0
100 200 300 400 500 600 700 800 900 1000 1100 1200
Counts vs. Mass -to-Charge (m/z)

x10 4 LLL
1.5 901.7869
1.45 b
1.4
1.35
1.3
1.25
1.2
1.15
1.1
1.05
1
0.95 902.7911
0.9 LLO
0.85 LnLnL LnLL 903.7681 Oxidized TAGs
0.8
0.75 897.7323 899.7323
0.7
0.65 LLS 917.7731
0.6 905.7637 913.8184
0.55 LnLnLn
0.5 895.7063 918.7772
0.45 911.7798 914.8205
904.7712
0.4
910.7897
0.35 900.7402 915.8070
898.7288 912.7953
0.3
0.25
0.2
0.15
0.1
0.05
0
895 896 897 898 899 900 901 902 903 904 905 906 907 908 909 910 911 912 913 914 915 916 917 918
Counts vs . Mass -to-Charge (m/z)

` (Patrizia Zara, 2008) (a); zoom of the mass range corresponding to


Fig. 16. FIA-ESI-Q-ToF high resolution mass spectrum of the extract of the paint sample Salto di Qualita
the oxidised TAGs (b).

from the paint on canvas Salto di Qualit by Patrizia Zara (Italy, of an oxidized alkyd paint. The comparison with the fatty acid
2008). prole obtained in the analysis of the commercial paint tubes
The GC/MS chromatogram of the paint sample is reported (Tables 2 and 3) conrms that a Winsor & Newton alkyd paint was
in Fig. 14 and the results are summarized in Tables 2 and 3. used: the sample from Zara paint contains 1,2-benzendicarboxylic
GC/MS analysis shows the presence of the aromatic acids 1,2- and ricinoleic acid, both found in the Winsor & Newton alkyd paint
benzendicarboxylic and 1,3-benzendicarboxylic acids, and of a fatty described in Section 3.2.
acid prole dominated by palmitic, stearic and ricinoleic acid. The HPLC prole of the paint sample is reported in Fig. 15.
Dicarboxylic acids (azelaic acid as the most abundant), unsatu- The glycerides prole is characterized by the presence of oxi-
rated fatty acids, and hydroxylated long chain fatty acids are also dized TAGs with m/z 917.7689 (PC18,OH C18,OH , [M+Na]+ ), 929.8361
present. The chromatographic prole is in agreement with that (SSC18,OH , [M+Na]+ ), m/z 945.8293 (SC18,OH C18,OH , [M+Na]+ ),
J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480 79

961.8058 (C18,OH C18,OH C18,OH , [M+Na]+ ) deriving from the oxi- the main component of the paint tubes. As for the Ferrario resins,
dation process of the alkyd resin. A small amount of free, no differences in the composition were identied between the
non-crosslinked triglycerides were identied, mainly LnLnLn, three resins with different pigments.
LnLnL, LnLL, LLL, LLP, LLO, LOP, LLS and OLS. No aromatic fraction was identied in the Kremer alkyd oil,
Comparing the relative abundances of the non-oxidized TAGs thus suggesting that this material is not an alkyd resin, but an
to the three reference materials (Table 4), the prole of Zara paint industrially modied oil. GC/MS analysis revealed the presence
sample shows striking similarities with the Winsor & Newton alkyd of oleic, linoleic, ricinoleic and undecanoic acids. The DAG and
paint. In particular, the presence of LnLnP, a marker detected only in TAG proles, including the presence of 12-acyltriglycerides and
the Winsor & Newton Grifn fast drying oil color, supports our iden- 12-12 -acyltriglycerides, enabled us to identify castor oil as the
tication of the trademark. Our hypothesis was further conrmed main raw material in the production of the oil, whose compo-
by the artist, who provided the information that the artwork was nents were subjected to dehydration and transesterication at a
indeed painted using Winsor & Newton Grifn alkyd Grifn Fast high temperature. The presence of undecanoic acid in the GC/MS
Drying Oil Colour paint tubes. prole and of TAGs containing undecanoic acid in the HPLC chro-
The triglyceride prole was also characterized by FIA-ESI-Q-ToF. matogram and FIA-ESI-MS mass spectra suggests that this free
The mass spectrum (Fig. 16a) shows the presence of m/z 929.8361, acid was added during the synthesis.
m/z 945.8293, m/z 961.8058 as main ions, characteristic of satu-
rated oxidized TAGs. In the mass range m/z 890920 (Fig. 16b) The results obtained by FIA-ESI-Q-ToF showed a high degree
the main observed ions are: m/z 895.7063 (LnLnLn, [M+Na]+ ), m/z of coherency with the TAG proles obtained by HPLCESI-Q-ToF.
897.7323 (LLnLn, [M+Na]+ ), m/z 899.7323 (LnLL, [M+Na]+ ), m/z These results highlight the suitability of this analytical technique
901.7869 (LLL, [M+Na]+ ), m/z 903.7681 (LLO, [M+Na]+ ) and m/z for the rapid characterization of triglycerides and polymeric addi-
905.7637 (LLS, [M+Na]+ ). In the mass range m/z 910920, ions are tives in unknown samples, in a shorter analysis time and a simpler
attributable to unsaturated oxidized TAGs with different number instrumental optimization than HPLC separation.
of hydroxyl groups. The application of the three combined mass spectrometry tech-
niques on the paint sample collected from the artwork Salto di
5. Conclusions qualit by Patrizia Zara (2008) proved the efciency of the analyt-
ical method for the characterization of alkyd resins in real samples.
The proposed analytical approach, based on the integration of The procedure is thus suitable for the characterization of aged alkyd
GC/MS, HPLCESI-Q-ToF and FIA-ESI-Q-ToF analyses, proved to be resins and for discriminating between different trademarks.
very powerful in fully characterizing the chemical composition In conclusion, the proposed analytical approach can be exploited
of three different sets of industrial oil-based paint materials. The for evaluating the state of conservation of artworks, for aging stud-
proposed method also enabled us to understand the processes ies, and for investigating curing and oxidation processes.
exploited to produce these materials.
GC/MS analysis after saponication assisted by microwaves and Acknowledgment
derivatization enabled us to identify the fatty acid prole and the
aromatic fraction of the paint materials. HPLCESI-Q-ToF enabled The authors gratefully acknowledge the COPAC project Pre-
us to determine the triglyceride proles of the three sets of materi- ventive Conservation of Contemporary Art, funded by PAR-FAS
als. FIA-ESI-Q-ToF proved capable to yield information on the TAG Regione Toscana 20112013, for nancial support.
proles directly in hexane extracts without chromatographic sep-
aration, and to identify additives, even in an oxidized paint layer
from an artwork. The results highlight the variety of the chemical References
compositions of commercial products of this category. Thus, their
[1] T. Learner, Analysis of Modern Paints, Getty Publication, Los Angeles, 2004.
characterization in artworks appears fundamental in order to plan
[2] A. Burnstock, K.J.V.D. Berg, S.D. Groot, L. Wijnberg, in: T. Learner (Ed.), Reprints
preventive conservation and choose specic cleaning protocols. of the Modern Paints Uncovered Conference, Getty, Los Angeles, 2008, pp.
The main features of each alkyd resin can be summarized as 177188.
[3] A. Spyros, J. Appl. Polym. Sci. 88 (2003) 18811888.
follows:
[4] R. Ploeger, D. Scalarone, O. Chiantore, J. Cult. Herit. 9 (2008) 412419.
[5] R. Ploeger, D. Scalarone, O. Chiantore, Polym. Degrad. Stab. 94 (2009)
20362041.
The Ferrario Alkyd resin was produced by transesterication in
[6] S. Wei, V. Pintus, M. Schreiner, J. Anal. Appl. Pyrol. (2013), http://dx.doi.org/
presence of linseed and soybean oil. GC/MS and HPLC analy- 10.1016/j.jaap.2013.05.028 (in press).
sis revealed the presence of palmitic, stearic, oleic and linoleic [7] M.R. Schilling, J. Mazurek, T.J.S. Learner, Modern Paints Uncovered: Proceedings
from the Modern Paints Uncovered Symposium, L.A. Getty Conservation Insti-
acids, and LL, LO, LnLnLn, LLnLn, LnLL, LLL, PLL, LLO, LOP, LLS,
tute, 2007, pp. 129139.
OOP and OLS, respectively. FIA analysis showed the presence [8] R. Ploeger, S. Musso, O. Chiantore, Prog. Org. Coat. 65 (2009) 7783.
of PEG used as an additive. The aromatic component was 1,3- [9] M. Lazzari, O. Chiantore, Polym. Degrad. Stab. 65 (1999) 30033313.
[10] S.S. Narine, X. Kong, Vegetable Oils in Production of Polymers and Plastics, John
benzendicarboxylic acids. The three selected resins with different
Wiley & Sons, Inc., 2005.
pigments show the same chemical composition. [11] R.J. Hamilton, C. Kalu, E. Prisk, F.B. Padley, H. Pierce, Food Chem. 60 (1997)
The Winsor & Newton resin was found to have a very similar glyc- 193199.
erolipid composition to Ferrario alkyd, addressing to linseed and [12] H. Mutlu, M. Meier, Eur. J. Lip. Sci. Technol. 112 (2010) 1030.
[13] D. Scalarone, M. Lazzari, O. Chiantore, J. Anal. Appl. Pyrol. 58 (2001) 503512.
soybean oil. GC/MS analysis highlighted the presence of palmitic, [14] M. Holcapek, P. Jandera, P. Zderadicka, J. Chromatogr. A 1010 (2003)
stearic, oleic, linolenic, linoleic and ricinoleic acids. However 195215.
the absence of TAGs containing a ricinoleyl substituent in the [15] J.T. Lin, A. Arcinas, L.R. Harden, C.K. Fagerquist, J. Agric. Food Chem. 54 (2006)
34983504.
HPLCMS chromatogram suggested that free ricinoleic acid was [16] F.J. Palmer, A.J. Palmer, J. Chromatogr. 465 (1989) 369377.
added to the alkyd resins to improve their physical proprieties. [17] A. Stolyhwo, H. Colin, G. Guiochon, Anal. Chem. 57 (1985) 13421354.
The aromatic components were 1,2-benzendicarboxilyc and 1,3- [18] A. Zeb, M. Murkovic, Eur. J. Lip. Sci. Technol. 112 (2010) 844851.
[19] H.R. Mottram, S.E. Woodbury, R.P. Evershed, Rapid Commun. Mass Spectrom.
benzendicarboxylic acids. Neither FIA nor HPLC analysis revealed 11 (1997) 12401251.
the presence of other additives. The FIA results suggest that the [20] F. Saliu, F. Modugno, M. Orlandi, M.P. Colombini, Anal. Bioanal. Chem. 401
resin was produced by transesterication and the drying oil was (2011) 17851800.
80 J. La Nasa et al. / Analytica Chimica Acta 797 (2013) 6480

[21] I. Degano, J.L. Nasa, E. Ghelardi, F. Modugno, M.P. Colombini, J. Chromatogr. A [29] I. Bonaduce, M.P. Colombini, I. Degano, F.D. Girolamo, J.L. Nasa, F. Modugno, S.
(2013), http://dx.doi.org/10.1016/j.chroma.2013.08.015 (in press). Orsini, Anal. Bioanal. Chem. 405 (2013) 10471065.
[22] A. Andreotti, I. Bonaduce, M.P. Colombini, G. Gautier, F. Modugno, E. Ribechini, [30] J.N. Low, C. Scrimgenour, P. Horton, Acta Crystallogr. 61 (2005).
Anal. Chem. 78 (2006) 44904500. [31] O.D. Shreve, M.R. Heether, H.B. Knight, D. Swern, Anal. Chem. 22 (1950)
[23] M.P. Colombini, A. Andreotti, I. Bonaduce, F. Modugno, E. Ribechini, Acc. Chem. 12611264.
Res. 43 (2010) 715727. [32] S. Varray, J.L. Aubagnac, F. Lamaty, R. Lazaro, J. Martinez, C. Enjalbal, Analusis
[24] M.P. Colombini, F. Modugno, R. Fuoco, A. Giacomelli, E. Menicagli, Microchem. 24 (2000) 263268.
J. 67 (2000) 291300. [33] L.I. Miller, US4442256 A.
[25] M.P. Colombini, F. Modugno, R. Fuoco, A. Tognazzi, Microchem. J. 73 (2002) [34] W.J. Muizebelt, M.W.F. Nielen, J. Mass Spectrom. 31 (1996) 545554.
175185. [35] S.N. Modak, J.G. Kane, J. Am. Oil Chem. Soc. 42 (1965) 428432.
[26] L.C. Herrera, M.A. Potvin, J.E. Melanson, Rapid Commun. Mass Spectrom. 24 [36] Safety data sheet Winsor & Newton Grifn alkyd fast drying oil colour.
(2010) 27452752. [37] M. Aritomi, US4111871 A.
[27] J. Turk, F.F. Hsu, J. Am. Chem. Soc. 10 (1999) 587599. [38] C.H. Pohl, J.L.F. Kock, V.S. Thibane, Antifungal Free Fatty Acids: A Review, For-
[28] H. Kallio, K. Yli-Jokipii, J.-P. Kurvinen, O. Sjvall, R. Tahvonen, J. Agric. Food matex, Spain, 2011.
Chem. 49 (2001) 33633369.