RAPID COMMUNICATIONS IN MASS SPECTROMETRY, VOL.

11, 286–294 (1997)

Curie-point Pyrolysis/Gas Chromatography/

Mass Spectrometry in the Art Field. Part 3:
The Characterization of Some
Non-proteinaceous Binders
Roberto Stevanato,1 Manuela Rovea,1 Massimo Carbini,2 Donata Favretto3 and Pietro Traldi4*
1
Dipartimento di Chimica Fisica, Universitá di Venezia-Dorsoduro 2137, I-30123 Venezia, Italy
2
Istituto di Chimica Industriale, Universitá di Padova, via Marzolo 9, I-35100 Padova, Italy
3
CNR, Area di Ricerca, Corso Stati Uniti 4, I-35020 Padova, Italy
4
CNR, Centro di Studio sulla Stabilitá e Reattivitá dei Composti di Coordinazione, Via F. Marzolo 1, I-35100 Padova,
Italy

Curie-point pyrolysis/gas chromatography/mass spectrometry has been employed to characterize nine

non-proteinaceous media used in the past as binders in works of art. Obtaining their fingerprints (achieved by
both chromatographic patterns and mass spectral data of the individual components) is important in the
context of the building of a complete database to be used in an analytical approach to the field of museum
materials and restoration. © 1997 by John Wiley & Sons, Ltd.
Received 17 December 1996; Accepted 3 January 1997
Rapid Commun. Mass Spectrom. 11, 286–294 (1997)
No. of Figures: 7 No. of Tables: 5 No. of Refs: 23

In the complex field of art and restoration, particular
attention must be paid to the different materials which
were employed by the artists to produce their works of
art or which were added over the progress of the years.
Furthermore, the natural ageing of the materials of art
must be taken into account, i.e. the whole of the time-
dependent chemical modifications of the molecular
structures of the original materials. The complexity and
variety of these materials make the analytical approach
to their identification and characterization a puzzling
task.
From the chemical point of view, carbohydrates and
natural resins are often encountered as museum mate-
rials. In fact, their availability from natural sources and
their good adhesive properties made them attractive
materials for works of art.1
Among carbohydrates, the most important polysac-
charides, which were used as paint binders, include

Table 1. Sugar and uronic acid components of some gums.

Arabinose Rhamnose Galactose Mannose Glucose Xylose Fucose Glucuronic Galacturonic
Acid Acid
Gum Arabic ++ + ++ + +
Tragacanth + + + + +

Figure 1. Pyrogram obtained by Curie-point Py/GC/MS of starch (sample 1).

* Correspondence to: P. Traldi

CCC 0951–4198/97/030286–09 $17.50 © 1997 by John Wiley & Sons, Ltd.

 PY/GC/MS OF NON-PROTEINACEOUS BINDERS

Figure 2. Electron ionization mass spectra of components 1–12 detected in the pyrogram of Fig. 1.
287
288 PY/GC/MS OF NON-PROTEINACEOUS BINDERS

Figure 2. continued.
 PY/GC/MS OF NON-PROTEINACEOUS BINDERS 289

Figure 3. Pyrogram obtained by Curie-point Py/GC/MS of gum arabic (sample 2).

Figure 4. Pyrogram obtained by Curie-point Py/GC/MS of gum tragacanth (sample 3).

cellulose, starch, the plant gums and mucilages.
Whereas the first two are of simple and regular
composition, the gums and the mucilages are more
complex. Plant gums were employed as adhesives and
binders, in particular on watercolours (acquerelli) and
miniatures, while starch was used as an adhesive, often
mixed with other substances, such as siccative oils and
resins, to obtain more flexible preparations
(mestiche).
Natural resins, spontaneously exuded by a large
variety of plants, were used both as adhesives and
coatings. In particular, their presence often appears in
ancient formularies for protective films, plasters, adhe-
sive mixtures, solutions for consolidating and so on.
Most of them are chemical compounds of the terpenoid
class.
With respect to analytical work in the museum field,
different situations were encountered in the past when
dealing with carbohydrates or resins respectively.
Whereas for the former, good information could be
gained by a variety of techniques (colorimetric assays,2
infrared spectroscopy,3 acid hydrolysis followed by
chromatography4,5), for the latter, the detection and
identification of specific resins in paint media was not
possible before the use of high-resolution gas chroma-
tography,6,7 Fourier-transform infrared spectroscopy8
290 PY/GC/MS OF NON-PROTEINACEOUS BINDERS

Table 2. Components individually identified in the pyro- ocal assignments to the resin composition of art
grams of Gum Arabic (2) and Gum Tragacanth (3) materials, and have also improved the information
Retention time Mass/charge
+.
Elemental 2 3 obtainable from carbohydrate-based media,15 revealing
(min.) value of M composition
the possibility of obtaining characteristic fingerprints
0.76 74 C3H6O2 * *
4.1 128 C6H8O3 * *
for the different materials.
5.8 128 C6H8O3 * *
All these recent techniques require only small
7.2 138 C7H8O3 * amounts of sample, avoid tedious and time-consuming
7.9 142 C6H6O4 * procedures, such as hydrolytic cleavage and/or deriva-
8.6 110 C6H6O2 * tization, and are amenable to both soluble and insolu-
9.2 140 C6H4O4 * ble samples.
9.7 154 C4H10O6 * * In this context, pursuing our interest in the applica-
10.8 152 C5H12O5 * * tion of Curie-point pyrolysis/gas chromatography/mass
11.5 110 C6H6O2 * spectrometry in the art field, we previously reported on
13.7 148 C5H8O5 * the results achieved in the characterization of siccative
15.1 102 C4H8O3 *
oils16 and proteinaceous binders17 and will now discuss
15.8 154 C4H10O6 * *
17.2 162 C6H10O5 * *
the data obtained by the same analytical approach on
17.6 102 C4H8O3 * other non-proteinaceous binders of the classes of
20.1 164 C6H12O5 * polysaccharides and natural resins, with the aim of
21.2 178 C6H10O6 * * obtaining a more complete ‘database’ to be employed
21.9 228 C8H20O7 * in the characterization of real samples of art material.
22.8 148 C5H8O5 *
24.6 186 C9H14O4 * *
25.1 242 C8H18O8 * EXPERIMENTAL
25.3 256 C9H20O8 * *
26 192 C7H12O6 * Starch (1), gum arabic (2), gum tragacanth (3), dammar
29.77 284 C10H20O9 * * (4), mastic (5), sandarac (6), colophony (7) and benzoin
30.23 280 C10H16O9 * * (8) were commercially available products, used in the
field of restoration, purchased from Phase-Prodotti per
* indicates identified
il Restauro (Firenze, Italy), distributed onto glass
surfaces and aged for about one year under natural
and gas chromatography/mass spectrometry.9 More light.
recently, new techniques such as pyrolysis/gas chroma- All mass spectrometric measurements were per-
tography,10 pyrolysis/gas chromatography/mass spec- formed on a Fisons MD 800 (Altrincham, UK) GC/MS
trometry,11,12 ion-source pyrolysis/mass spectrometry13 system operating in electron ionization conditions
and simultaneous pyrolysis-methylation/gas chroma- (70 eV, 100 µA) and linked with a Horizon (Heathfield,
tography/mass spectrometry14 have afforded unequiv- UK) Curie-point pyrolyzer. A magnetic iron wire with

Figure 5. Pyrogram obtained by Curie-point Py/GC/MS of (a) dammar (sample 4); (b) mastic (sample 5); (c) sandarac (sample 6) and (d)
colophony (sample 7).
 PY/GC/MS OF NON-PROTEINACEOUS BINDERS 291

Table 3. Components individually identified in the pyro- RESULTS AND DISCUSSION

grams of dammar (4), mastic (5) and sandarac (6)
Retention time Mass/charge Elemental 4 5 6
Pyrolysis/mass spectrometry has been widely and suc-
(min.) value of M
+.
composition cessfully employed in the characterization of large,
4.02 172 C10H17Cl * complex molecules when the size and/or the chemical
5.48 172 C10H17Cl * characteristics of the compounds do not allow a direct
7.2 150 C10H14O * mass spectrometric characterization of the intact form.
8.2 not present in C13H22O * * It has been used effectively in the field of art and
mass spectrum restoration, leading in many cases to the unequivocal
9.3 174 C13H18 * characterization of substrates of interest.
11.6 176 C13H20 * * In particular, in the characterization of binders,
12.7 190 C13H18O * *
pyrolysis/gas chromatography/mass spectrometry (Py/
15.9 200 C12H24O2 *
17.1 172 C13H18O * *
GC/MS) led to interesting results, giving rise to
21.8 228 C14H20O2 * * * effective fingerprints for the substrates. In fact, while
22.9 222 C15H26O * * the GC analysis affords highly reliable results, leading
24.3 242 C15H30O2 * * to a characteristic chromatographic profile for each
24.9 272 C20H32 * original material, mass spectrometry gives additional
25.7 272 C20H32 * parameters for the structural identification of the
27.6 256 C16H32O2 * * * different pyrolysis products and can be employed for
29 270 C17H34O2 * * * the identification, in the complex pyrolysis mixture, of
31 284 C18H36O2 * * * selected molecules by means of multiple-ion detection.
31.7 280 C18H32O2 *
The use of a Curie-point pyrolyzer (based on the direct
38.7 302 C20H30O2 *
43.5 264 C17H28O2 * *
deposition of samples on magnetic iron wires of
selected alloys which exhibit precise Curie tempera-
* indicates identified tures when immersed in an RF field)18 improves the
analytical performances of the Py/GC/MS method,
avoiding the intrinsic variability of the heating coil
a Curie-point at 610 °C was used as a support for the system and the consequent uncertainity about the exact
different samples and the pyrolysis time was set at 1s. temperature experienced by the samples.
The gas chromatographic conditions were as follows: The non-proteinaceous materials of natural origin
column DB17, 15 m long × 250 µm i.d., film thickness studied in the present investigation were employed,
0.5 µm; pyrolyzer interface 250 °C, injector 250 °C, especially in the past, as binders in paint media.
transfer line 270 °C, oven temperature ramp from 80 to Samples 1–3 are polysaccharides. In particular, gums 2
250 °C at a rate of 4 °C min–1. To afford proper and 3 are amorphous materials originating from Acacia
deposition on magnetic iron wires, samples were Senegal and from Astragalus (Leguminosae) respec-
suspended in an aqueous solution of 1% trifluoroacetic tively. They are constituted as polymers of different
acid. simple sugars, some of them containing carboxylic

Table 4. Components individually identified in the pyrograms of colophony

(7)
Retention time Mass/charge Elemental Structural Fit*
+.
(min.) value of M composition assignment
8.00 204 C15H24 Aromadendrene 894
9.77 204 C15H24 (+) Iso-longifolene 856
10.1 204 C15H24 Juniprene 921
11.152 204 C15H24 Alpha-humulene 930
12.63 204 C15H24 Alpha-murolene 956
13.686 204 C15H24 Delta-cadinene 921
14.45 202 C15H22
16.77 220 C15H24O Caryophyllene 789
oxide
16.98 222 C15H26O Longiborneol 915
19.43 220 C15H24O
19.9 220 C15H24O Longifolene aldehyde 818
24.6 272 C20H32
28.9 272 C18H26O3 Methyl abietate 721
29.9 254 C18H22O
30.4 290 C20H34O
31.8 272 C20H32 Isopimaradiene 864
32.3 286 C20H30O
33.9 286 C20H30O
34.4 288 C20H32O
36.9 302 C20H30O2
* Fit obtained by library search program contained in FISONS MD800 Mass Lab
software package
292 PY/GC/MS OF NON-PROTEINACEOUS BINDERS

Figure 6. Pyrogram obtained by Curie-point Py/GC/MS of benzoin (sample 8).

Table 5. Components individually identified in the pyrogram of benzoin (8)

Retention time Mass/charge Elemental Structural Fit*
(min.) value of M+. composition assignment

1.75 104 C8H8 1,3,7-octatrien-5-yne 980

3.27 94 C6H7O Phenol 932
4.88 108 C7H8O 2-hepten-4-ynal 907
7.57 138 C8H10O2 Benzene-1,2 dimethoxy 955
9.10 106 C7H6O Benzaldehyde 948
9.80 122 C7H6O2 Benzoic acid 975
11.42 150 C9H10O2 Ethanone, 1-(4 methoxy 912
phenyl)
11.70 78 C6H6 Benzene 910
12.67 134 C9H10O Cinnamyl alcohol 927
13.53 132 C9H8O Tricyclononadienone 894
15.46 164 C10H12O2 4-phenylbutyric acid 962
20–23 148 C9H8O2 Cinnamic acid 938
31.9 165 C8H10NO2 Nitrocumene 966
33.70 238 C16H14O2 Cinnamyl benzoate 981
34.45 238 C16H14O2 Benzyl cinnamate 966
41.8 284 C17H16O4 Coniferyl benzoate 974
43.78 138 C10H18 Octadiene-4,5-dimethyl 936
* Fit obtained by library search program contained in Mass Lab software package of
Fisons MD800

groups often as Ca, Mg or K salts. Their content of the
different sugars and uronic acids is summarized in Table
1.1
These materials are usually water soluble and are
found on the market with added preservatives, to avoid
microbial decomposition, and with moisteners to
decrease their fragility. Their main use is as adhesive
binders in paintings with a light support (e.g. paper)
and as mordants for gold. They were often employed to
form emulsions with oils, egg and casein.
Starch, sample 1, was obtained from rice and is a
relatively simple polysaccharide. In fact, it consists of
two regular polymers of glucose: amylose and amylo-
pectin. The former is a linear polymer with an α-glyco-
sidic bond, while the latter has a branched structure.
The proportions of these two fractions depends on the
natural source of the starch. Starch has been employed
in painting backgrounds and as an ingredient of relining
adhesives.
The chromatogram of the pyrolysis products of
compound 1 is shown in Fig. 1. As can be seen, a large
number of pyrolysis products are present. Most of these
have already been described in studies performed by
in-source pyrolysis/mass spectrometry employing dif-
ferent ionization methods.19–21 As an example, the mass
spectra of the most abundant compounds are reported
in Fig. 2, together with the most reasonable elemental
formula of the molecular species, obtained by compar-
ison with literature data.
The pyrogram of gum arabic (sample 2) is reported in
Fig. 3 while the pyrogram of tragacanth (3) is shown in
Fig. 4. The presence of different sugars in the polymeric
chain (see Table 1) strongly affects the production of
pyrolysis products. In fact, only a few species are
analogous to those already detected among the pyr-
olysis products of starch. The elemental compositions
assigned to the pyrogram components of gum arabic
and tragacanth are reported in Table 2 together with
their retention times and the mass values of the
molecular species.
Comparison of the pyrolysis chromatograms of the
three different polysaccharides analysed suggests that,
 PY/GC/MS OF NON-PROTEINACEOUS BINDERS
Figure 7. Pyrogram obtained by Curie-point Py/GC/MS of shellac (sample 9).
even though some of the pyrolysis products are
common to all three samples, the general appearances
of the pyrograms are different, due to the presence of
specific components, as well as to the different relative
abundances of those present in common.
Natural resins are natural by-products of tree and
plant metabolism, and are exuded spontaneously or are
collected by tapping. Most of them have the property of
forming films which were used as adhesives or coatings.
Their chemical compositions are mainly based on
polyterpenoids of different classes. The monoterpenoid
content varies from species to species and also within
the same species. Consequently, the resins represent
quite a complex substrate for investigation. However,
Py/GC/MS is highly effective in the characterization of
resins vs. other materials. In Fig. 5 are reported the
pyrograms of dammar, mastic, sandarac and colophony
resins. At first glance, the pyrograms of samples 4, 5 and
6 are strongly similar, while that of colophony shows
unique characteristics.
By analysing in detail the pyrogram components and
their electron ionization mass spectra, the data
reported in Table 3 were obtained on the molecular
species, mass values and related elemental composi-
tions of the different pyrolysis products of dammar,
mastic and sandarac. From the data reported it follows
that mastic resin is easily distinguished from the two
others by the presence of specific pyrolysis products
with retention times of 4.02, 5.48, 7.20, 15.9, 24.9 and
25.7 min.
The similarity between samples 4 and 6 is greater;
however some differences can be found in the abun-
dances of some of the common pyrolysis products and
in the presence of a specific component at 9.3 min
present only in sample 6.
Colophony is the solid residue obtained by distilla-
tion of oil of turpentine. Its composition is therefore
different from that of the original resin. In fact, the
various acids originally present in the Pinaceae resins
(abietadienic, laevopimaric, palustric, abietic and neo-
abietic acid) are interconvertible through isomerization
293
of the double bond. Thus, the mixture formed during
heat treatment mainly contains abietic acid. By such
treatment, the formation of dehydro- and di-dehydro
abietic acids has also been described.22 These con-
siderations explain the differences between the pyro-
gram of 7 and those of 4–6 satisfactorily. The structural
assignments of the most abundant peaks of the coloph-
ony pyrogram are reported in Table 4. It should be
noted that, for the same elemental composition, a wide
variety of isomers is present, and only the most
abundant components have been listed in the Table.
In Fig. 6 the pyrogram of sample 8 is reported.
Benzoin differs from the resins discussed above in
chemical composition, because it is not a polyterpenoid
resin but is comprised of esters of aromatic acids
(benzoic and cinnamic) with aromatic alcohols. Ben-
zoin is, in fact, representative of the class of the so-
called balsamic resins. It was seldom used in the art
field, but was employed, dissolved in alcohol, mainly as
a varnish. In Table 5 are listed the components detected
in the pyrogram of sample 8; these allow a good
characterization of benzoin. In particular the abundant
(and tailing) peaks at 9.8 and 23.8 min have been
assigned to benzoic- and cinnamic acids respectively,
while coniferyl benzoate is responsible for the peak at
41.8 min.
Sample 9, shellac, is practically the only resin of
animal origin. In fact, it is produced by the insect Kerria
lacca (Kerr) which infests a variety of host trees. It is
comprised of low molecular weight polyesters of
different hydroxy acids which are soluble in alcohol
(70–80%), waxes that are insoluble in alcohol (6–7%),
and a dye that is soluble in water (4–8%). It was mainly
used in the formulation of red varnishes for furniture
and it was only rarely used in paintings as an adhesive
for wall paints. Its chemistry is complex and strongly
depends on the different host trees.23 The identification
of the different hydroxy acids constituting the poly-
esters has been made after saponification and derivati-
zation prior to GC analysis.
294 PY/GC/MS OF NON-PROTEINACEOUS BINDERS
Notwithstanding its chemical complexity, the pyro-
gram of shellac, reported in Fig. 7, is comparatively
simple, consisting mainly of only seven components,
four of which are particularly abundant.
From the data reported, it is evident that Curie-point
Py/GC/MS is a valuable tool for obtaining character-
istic patterns for the different materials analysed
without complex procedures of extraction, derivatiza-
tion and so on. The high reproducibility of the pyrolysis
conditions when using a Curie-point pyrolyser is
reflected in the reproducibility of the pyrograms
obtained. The specificity of the pyrogram patterns does
not rely on retention time only, but is greatly enhanced
by the electron ionization mass spectra of the different
components. In fact the chemical identification of the
pyrolysis products is easily obtained on this basis and
can be unequivocally related to the chemical structure
(and natural origin) of the different binders. Thus, the
distinction between polysaccharide binders (samples
1–3) and resins (samples 4–9) is immediate and
unequivocal. Furthermore, within the same class of
materials, balsamic resins are easily distinguished from
polyterpenoid resins on the basis of the different
chemical nature of the components identified. Poly-
terpenoid resins of the same chemical class but from
different sources can be distinguished, although more
cautiously, on the basis of some specific components
present in the complex mixture of polyterpenoid
products. In particular, this distinction was immediate
in the case of sample 5 vs. 4 and 6, but required more
careful data analysis in the case of sample 4 vs. 6.
Acknowledgements
We thank Phase-Prodotti per il Restauro for helpful collaboration.
This work was supported by grants from the Italian Consiglio
Nazionale delle Ricerche (CNR).
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