Maite Ibern-Gomez,
Olga J auregui,
and
Rosa Maria Lamuela-Raventos*
,
Nutrition and Food Science Department, Pharmacy Faculty and Scientific and Technical Services, University of Barcelona,
08028 Barcelona, Spain
Presentedinthispaper isanewmethodfor theidentifica-
tion of tartaric acid as a wine marker in archaeological
residues fromEgyptian vessels usingliquid chromatog-
raphywithmassspectrometryintandemmode(LC/ MS/
MS). Owingtothespecial characteristicsofthesesamples,
such as thedryness and thesmall quantityavailablefor
analysis, it was necessary to have a very sensitive and
highlyspecific analytical methodtodetecttartaric acidat
trace levels in the residues. Furthermore, an alkaline
fusion was carried out to identify syringic acid derived
frommalvidinasaredwinemarker, inadepositresidue
fromawinejar foundat thetombof kingTutankhamun.
Malvidin-3-glucoside, the main anthocyanin that gives
youngwines their red color, polymerizes with aginginto
morestablepigments. However, thepresenceofmalvidin
in ancient residues can be proved by alkaline fusion of
the residue to release syringic acid from the pigment,
whichhasbeenidentified, herefor thefirsttime, byusing
theLC/ MS/ MSmethod revealingthered grapeorigin of
an ancient Egyptian wineresidue.
In ancient Egypt, vines were grown throughout the country,
although the best wines came from the Nile River Delta and the
Western oasis.
1
In fact, wine was a product of great importance,
offered in funerary rituals and in temples to worship gods and
consumed daily by the upper classes during meals and parties.
1
Since the Early Dynastic period (2920-2575 BC
2
) wine jars were
placed in tombs as funerary meals, some with engraved inscrip-
tions. From the Old Kingdom (2575-2134 BC
2
) to the New
Kingdom (1550-1070 BC
2
) periods, tomb walls of the nobles were
decorated with scenes including viticulture and wine-making.
Egyptian mythology even related the red color of the Nile during
flooding to the color of wine.
1
The New Kingdom wine jars were
labeled with product, year, source, and even the name of the vine
grower,
3,4
but they did not mention the type (color) of wines
contained. Most of the labeled jars are nowonly broken fragments,
but some are completely preserved. Despite that, residues from
archaeological vessels have been barely investigated.
Considering the special characteristics of archaeological samples,
our aim was to develop avery sensitive and highly specific method
for identification of wine markers that might be present in trace
quantities. In particular, tartaric acid, rarely found in nature in
sources other than grapes, has been reported as a wine marker
in ancient residues and could be preserved in the pottery because
it can be strongly absorbed on silicates by hydrogen bonding.
5
Analysis of ancient samples requires a very sensitive method in
order to minimize the amount of sample used.
6
Four analytical
methods (thin-layer chromatography,
7
gas chromatography,
7
dif-
fuse-reflectance Fourier transform infrared spectroscopy,
5,8,9
and
high-performance liquid chromatography with UV detection
9
) have
been applied for tartaric acid determination in archaeological
samples. However, all of them lack enough selectivity and
sensitivity for the size of samples available, so an improved method
was required. Liquid chromatography/ mass spectrometry in
tandem mode (LC/ MS/ MS) has become an ideal technique due
to its speed, sensitivity, and selectivity and a powerful tool for
identification based on retention times and fragmentation patterns
of the compounds during MS/ MS analysis apart from low
detection limits. Another important feature of triple quadrupole
MS instruments is that they provide the highest sensitivity in
multiple reaction monitoring (MRM) mode. When the compounds
are present at trace levels or the amount of sample available is
limited, an MRM assay is the method of choice because it provides
* To whom correspondence should be addressed. E-mail: lamuela@ub.edu.