The Analytical

Approach
Edited by Jeanette G. Grasselli

Papyrus
The Paper of Ancient Egypt
Papyrus Ebers (16th century B.C.) contains, in more than 100 columns,
10 000 medical recipes for treatment of all kinds of diseases
Egypt was not only the kingdom of
the pharaohs with their pyramids,
temples, tombs, mummies, and a mul-
tiform world of gods, but also the land
of officials, scribes, and the written
word (1). The importance of the latter
is evident from the texts and inscrip-
tions on papyrus, the "paper" of an-
cient Egypt. These papyri contained
texts referring to the public and pri-
vate life in ancient Egypt; they are the
written heritage of a culture that ex-
isted over thousands of years. The old-
est papyrus ever found originates from
the First Dynasty (3000 B.C.); the ear-
liest inscribed papyrus is assigned to
the Fifth Dynasty (2400 B.C.).
At the beginning of the 20th centu-
ry, scientific excavation campaigns by
archeologists in middle and upper
Egypt uncovered an unexpected, rich
cache of papyri writings, excellent-
ly preserved due to the dry Egyptian
climate and overlying desert sand.
These papyri are now located in Egyp-
tian collections in European museums,
and their availability for scientific ex-
amination allows us to learn much
about the age, composition, and pro-
cessing of this ancient paper. To ex-
amine these materials we selected a
number of different analytical tech-
niques: thermoanalytical methods—
thermogravimetric analysis (TG), dif-
ferential thermal analysis (DTA), and
thermal mechanical analysis (TMA);
mass spectrometry (MS); and optical
and electron microscopy. These tech-
niques required only small amounts of
the original ancient samples, yet pro-
vided much useful information. Before
we began our investigation, however,
we had to study the papyrus plant it-
self.
Cyprus Papyrus
Papyrus was grown in various parts
of the Near East and Egypt, including
the delta of the Nile. The stems, which
are used to make the writing material,
have a triangular cross section and
may reach a height of 3-6 m. Table I
shows the complete elemental analysis
of both ancient (1300 B.C.) and fresh
(1977) papyri.
The main components of the papy-
rus plant, cellulose, hemicellulose, and
about lignin, are shown in the photomicro-
graph of a section of fresh papyrus

1220 A · ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983 0003-2700/83/A351-1220$01.50/0
© 1983 American Chemical Society
 H. G. Wiedemann
Mettler Instrumente AG
CH-8606 Greifensee/Zurich
Switzerland

G. Bayer
Institute of Crystallography and Petrography
Swiss Federal Institute of Technology (ΕΤΗ)
8092 Zurich
Switzerland

Damaged painting in an ancient papyrus (Book of Death). The barge was originally painted with green copper acetate

stem and in the DTA curves of sam­ from ancient Egypt, one finds descrip­ cient Egypt (2). The following is taken
ples from different regions of the stem tions of all kinds of technical pro­ from a recent English translation by
(Figure 1). The upper curve (a) is from cesses and recipes for a variety of H. Rackham of the fourth volume of
a collateral bundle, which contains products. However, even though papy­
more "incrust" (lignin) than cellulose. rus was used in large quantities, the
The middle curve (b) corresponds to details of its original manufacturing Table I. Elemental Analysis
the cellulose region that surrounds the process are missing. Since papyrus of Papyrus
collateral bundle. Cellulose and hemi- was rather expensive, perhaps the pro­
Ancient Fresh
cellulose predominate; and the shoul­ cess was kept secret to preserve a mo­ sample papyrus
der on the lignin peak indicates the nopoly for its production and export. ( % by ( % by
presence of both monomeric and di- The only picture that gives some in­ Elements weight) weight)
meric phenols. The material of the formation, at least of the first steps Oxygen 38.56 52.70
third sample was taken from the inter­ during the fabrication of papyrus, was Carbon 36.22 40.27
mediate layer between the collateral a mural discovered in the tomb of Hydrogen 4.78 4.37
bundle and the cellulose region. Its Puy-em-Re. It shows the harvesting of Nitrogen 1.55 0.95
lower curve (c) shows more cellulose papyrus, plus the bundling and de­ Sulfur 0.55 0.40
and hemicellulose than monomeric Silicon 7.17 0.54
barking of the stems. A detailed de­ Iron 1.75 trace
phenols of lignin. scription of the subsequent produc­ Aluminum 4.05 0.009
tion of "papyrus paper" may be found, Calcium 2.64 0.14
How Was Papyrus Made? however, in Pliny's "Natural History" Magnesium 0.83 0.07
Looking through the many exam­ (80 A.D.) in which he also refers to pos­ Sodium 1.43 0.43
ples of original literature and pictures sible manufacturing processes in an­

ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983 · 1221 A

 this encyclopedia (3): "The process of
making paper from papyrus is to split
it with a needle into very thin strips
made as broad as possible, the best
quality being in the center of the
plant, and so on in the order of its
splitting up. Paper of all kinds is
'woven' on a board moistened with
water from the Nile, muddy liquid
supplying the effect of glue. First an
upright layer is smeared onto the
table, using the full length of papyrus
available after the trimmings have
been cut off at both ends, and after-
wards cross strips complete the lat-
ticework. The next step is to press it in
presses, and the sheets are dried in the
Magnification 40x sun and then joined together. There
are never more than twenty sheets to a
Monomeric Lignin
roll." This description is historically
Polymeric Lignin very valuable but the accuracy of
Hemicellulose Pliny's statement about the gluing ac-
Cellulose tion of the muddy Nile water is ques-
tionable (especially since we discov-
ered that filtered Nile water produces
the same effect).
Exotherm According to research by Hepper
and Reynolds (4), it is likely that the
adhesion between the individual pa-
pyrus strips is provided by the gum-
like substances from the cell sap of the
pith of papyrus. These are identified
as water-soluble polymers of galac-
tose, arabinose, and a trace of rham-
nose—constituents that are also found
in other vegetable gums. However,
other investigations by Ragab (5) con-
0.5 mW cluded that the adhesion between the
papyrus strips has more of a physical
than a chemical nature. According to
Ragab the physical pressing together
of the crosswise-laid sheets causes the
parenchymatous tissues to dovetail
and merge. This becomes permanent
during the drying and shrinking of the
strips, thus ensuring good adherence.
From his own investigations Ragab
further concluded that starch was not
used as a gluing substance in ancient
Egypt. However, our microscopic in-
vestigations proved that starch was
definitely used in ancient Egyptian
papyri at least until 300 B.C. Microsco-
Figure 1. Photomicrograph (40x) of a section of fresh papyrus stem and different py of over 50 microtome cuts from
regions of the stem. DTA curves in oxidizing atmosphere of (a) collateral bundle; various ancient papyri showed that
(b) cellulose region surrounding collateral bundle; (c) intermediate layer they all contained a layer of starch ad-
hesive between the papyrus layers.
Figure 2 shows both a recent papyrus
(1976) and an ancient papyrus (344
Table II. Composition (Wt B.C.), and the presence of starch in
the latter is very evident. Our own
from TG Measurements % ) of Ancient Papyri Determined thoughts are that perhaps the use of
Sample Ash starch was discontinued because of
weight Water Cellulose Lignin content
Papyrus the loss of the knowledge of the pro-
(me) (%> (%) <%) <%) cess or the lack of starch due to a bad
1900 B.C. 1.045 4.93 54.81 32.77 7.49
1.285 6.77 58.14 27.83 7.26
corn harvest.
344 B.C.
5 B.C. 2.368 7.47 62.04 22.42 8.07 Thermoanalytical Investigations
578 A.D. 2.430 7.12 53.29 24.81 14.78
Sicily, 1977 A.D. 3.157 4.85 53.12 28.86 13.21 Typical TG and DTG curves of a
Egypt, 1977 A.D. 1.424 4.92 68.96 24.02 2.04 papyrus sheet are shown in Figure 3.
The oxidative degradation of cellulose
HHHHHHHHHBBBI occurs at about 250-350 °C followed

1222 A · ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983

Figure 2. Photomicrographs of (a) microtomed papyrus
sheet (1976) with no adhesive in transmitted light with
crosswise arranged papyrus strips (2x); (b) ancient pa-
pyrus sheet (344 B.C.) with adhesive starch layer (500x)

by that of lignin at 380-450 °C (6).

Heating in an inert atmosphere (nitro-
gen or argon) produced a very un-
characteristic DTG curve. Only the
combustion in air allowed differentia-
tion between various kinds of papyri
based on the position, shape, and
height of the bands.
The position and the height of the
lignin peak especially are very sensi-
tive to the processing of the papyrus,
to its age, and to its state of preserva-
tion (7). Table II shows the composi-
tion of several different papyri, in-
cluding two recent samples from Sicily
and Egypt (8), in terms of their H 2 0 ,
cellulose, and lignin content as de-
rived from TG/DTG measurements.
The Sicilian and Egyptian material
showed distinctly different behavior
during the decomposition process.
Corresponding DTA curves (Figure 4)
show that the lignin peak of the Egyp-
tian material is much smaller than
that of the Sicilian material. These
two curves represent the two basic
types of DTA curves that were ob-
served for most of the ancient papyri.
To determine if differences in these
curves could be caused by different
treatments, we produced papyrus
sheets with two different pretreat-
ments—pressing and beating. Figure 5
shows the effect of the pretreatment
on the shape of the peaks. The differ-
ence between the lignin peaks of the
pressed (Figure 5a) and of the beaten
(Figure 5b) papyri is caused by me- Figure 3. Typical (a) TG and (b) DTG curves of an ancient (1900 B.C.) papyrus sheet
chanical destruction of the material, (heating rate: 6 °C/min)

1224 A · ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983

Figure 4. DTA curves of recent papyrus sheets from Egypt
and Sicily (sample weight: 1.75 mg; heating rate:
0.5 °C/min)
Figure 5. DTA curves of (a) pressed and (b) beaten papyrus
sheets (heating rate: 0.5 °C/min)
which results in a lowering of the heat
of combustion. The small endothermic
peak developed at 140 °C (Figure 5b)
is caused by the dehydration of calci­
um oxalate monohydrate. This obser­
vation agrees with the well-known fact
that fast-growing plants such as sedge,
reed, and papyrus contain oxalic acid.
Calcium oxalate is then formed by re­
action with calcium assimilated from
the soil and incorporated into the cell
walls. Larger amounts of calcium oxa­
late may be generated during the
beating process by reaction of residual
oxalic acid in the cell walls with the
calcium-containing water in the capil­
laries of the plant. The additional exo­
thermic DTA peak in the temperature
range 320-390 °C is due to the decom­
position of calcium oxalate into the
carbonate, with evolution of carbon
dioxide.
To determine how the lignin peak
changes with age, we asked the Egyp­
tian Museum in Berlin for dated sam­
ples from 600 B.C. to 600 A.D. DTA
curves of these samples are shown in
Figure 6. These curves show that the
lignin peak decreases slightly with in­
creasing age of the sample.
The yellow-brown coloration, which
is almost always present in ancient pa­
pyrus materials, probably is caused by
a higher degree of dimerization of the
lignin. These colorations could be sim­
ulated on fresh papyrus. Papyrus
strips heated for 1 h from 100-220 °C
showed increasing intensity of brown
coloration. DTA curves of these sam­
ples showed that the lignin peak de­
creases with increasing temperature
Figure 6. DTA curves of dated ancient while the cellulose peak remains prac­
papyri (sample weight: 2.5 mg; heating tically unchanged. Papyrus that has
rate: 0.5 °C/min) been heated does not become as in­
1226 A · ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983
tensely dark because the heating de­
stroys part of the lignin, which is
washed out and therefore not avail­
able for dimerization during heating.
Mass Spectrometric Investigations
Another useful method for our in­
vestigations was pyrolysis mass spec­
trometry (MS). The amount of sample
necessary for such studies is extremely
small, 10-50 μξ. The sample is heated
to 500 °C in the oven, which is con­
nected to the mass spectrometer. The
pyrolyzates are continuously di­
rected toward the ionization source.
This technique allows the integrat­
ing registration of all volatile pyroly­
zates generated in the complete pyrol­
ysis procedure.
Typical mass spectra recorded dur­
ing the pyrolysis of cotton cellulose,
lignin, and the ancient papyrus West-
car are shown in Figure 7. The spec­
trum of cellulose indicates the pres­
ence of levoglucosane (m/z 162) and
its decomposition products (m/z 144,
126), furan (m/z 98), acetic acid
(m/z 60), and ionized methanol
(m/z 31). The spectrum of lignin
shows the presence of coniferyl alco­
hol, a lignin monomer (m/z 180), as
well as other substituted lignin phe­
nols.
To investigate the effect of age on
cellulose structure we recorded mass
spectra of pyrolysis products from cot­
ton cellulose and papyri of various
ages. Peaks with m/z 162 and 144 de­
creased or disappeared with increasing
age, indicating that levoglucosane, the
monomeric building block of cellulose,
undergoes single or multiple dehydra­
tion with time. Eventually, it is trans­
formed to levoglucosenone (m/z 126).
Figure 7. M a s s s p e c t r a of p y r o l y s i s p r o d u c t s f r o m c o t t o n , lignin, and a n c i e n t p a p y r u s
The spectrum from the papyrus West-
car illustrates this dehydration.
TMA Studies
The swelling behavior of papyri was
also investigated in relation to age by
subjecting a number of papyri to dy-
namic TMA. Figure 8a shows the TMA
cell. The sample is placed between the
vitreous silica platform and movable
S1O2 rod and subjected to a variable
load. After equilibration (3-5 min),
water is added to the dish. Figure 8b
shows the swelling behavior of a fresh
and an ancient papyrus sample. First
there is a sudden contraction due to
the imbibition with water, followed by
a parabolic swelling curve. Taking the
fresh papyrus as a reference (100%),
the ancient papyrus (578 A.D.) shows
swelling on the order of 5-6%. Further
experiments with ancient papyri from
different periods showed that papyri
Figure 8. (a) T M A c e l l and (b) T M A c u r v e s of p a p y r u s
1228 A · ANALYTICAL CHEMISTRY, VOL. 55, NO. 12, OCTOBER 1983
from about 1000 B.C. swell about 2-3%
whereas papyri older than 1500 B.C.
show no expansion at all (9).
D e c a y of P a p y r i
A serious problem encountered with
historic papyri involves their state of
preservation, since they are usually
very fragile. The gradual browning of
papyrus has been mentioned already.
In addition, many papyri are also par-
tially destroyed by fungi, which can be
identified by electron microscopy. It is
not possible to use DTA in such stud-
ies since there is an overlapping of the
peaks of cellulose and of the chi-
tin, a celluloselike biopolymer that
occurs typically in many fungi and is
characterized by its high chemical re-
sistance. Blue-green algae have also
been found on some of the ancient
papyri, in particular on the papyrus
Ebers (2000 B.c.) (10).
Another source of severe damage to
ancient papyri was the unintentional
use of corrosive pigments. The green
color (verdigris, basic copper acetate)
was especially destructive, since it de-
composes by gradually splitting off
acetic acid, causing degradation of the
papyrus (11). Many ancient papyri
have been destroyed by this reaction;
one example is the papyrus Book of
Death, shown on p. 1221 A.
Conclusions
Our work included a number of dif-
ferent techniques, all of which con-
tribute to a better understanding and
knowledge of the manufacture and
composition of one of our first "pa-
pers." Thermoanalytical method stud-
ies like DTA, TG, TMA, and pyrolysis
MS show that the proportions of the
main constituents of papyrus—cellu-
lose and lignin—vary with age, manu-
f a c t u r i n g process, a n d e n v i r o n m e n t a l
effects. Generally, cellulose is the more
s t a b l e c o m p o n e n t . In all p a p y r i t h e
H2O c o n t e n t r e m a i n s r a t h e r c o n s t a n t
a t ~ 1 0 wt %. P a p y r i t h a t have been
b e a t e n show t h e typical T G c a l c i u m -
o x a l a t e p e a k a t ~ 1 4 0 °C a n d a d e -
crease in t h e lignin c o n t e n t in relation
t o t h e cellulose. T h i s decrease of lignin
is also found w h e n p a p y r i are partially
d e s t r o y e d by t h e effect of fungi.
F u r t h e r m o r e , t h e s t u d i e s show t h a t
t h e yellow-brown coloration of a n c i e n t
p a p y r i is p r o b a b l y d u e t o t h e higher
degree of p o l y m e r i z a t i o n of t h e lignin
c o n s t i t u e n t s . T h i s effect can be accel-
e r a t e d by higher t e m p e r a t u r e s . T h e
b r o w n i n g effect m a y be i n h i b i t e d t o
s o m e e x t e n t w h e n t h e p a p y r i are beat-
en d u r i n g their m a n u f a c t u r e . S u c h
t r e a t m e n t d e s t r o y s p a r t of t h e lignin,
which is w a s h e d o u t a n d no longer
available for polymerization.
Microscopic investigations prove
t h a t all t h e a n c i e n t p r e - C h r i s t i a n pa-
pyri u p to 350 B.C. c o n t a i n e d a layer of
s t a r c h . Younger p a p y r i , however, were
m a n u f a c t u r e d w i t h o u t t h e aid of a
starch binder.
Finally, investigations on t h e swell-
ing behavior of p a p y r i show t h a t t h i s
p r o p e r t y decreases with increase in
age of t h e p a p y r i a n d is practically
zero for p a p y r i from p e r i o d s before
1500 B.C.
Acknowledgment
W e t h a n k William K. S i m p s o n , M u -
s e u m of F i n e A r t s , Boston, for t h e
s a m p l e of t h e p a p y r u s Reissner, D.
D e b e s , K. M a r x University, Leipzig,
G.D.R., for s a m p l e s a n d p h o t o g r a p h s
of t h e p a p y r u s E b e r s , a n d t h e B i b -
l o t h e c a B o d m e r i a n a , Cologny Geneva,
S w i t z e r l a n d , for p e r m i s s i o n t o r e p r o -
d u c e t h e p h o t o g r a p h of t h e p a p y r u s
B o o k of D e a t h . We also t h a n k J. S e t t -
gast, d i r e c t o r of t h e E g y p t i a n M u s e -
u m , W e s t Berlin, for t h e p a p y r u s s a m -
ples m e n t i o n e d in Figures 2, 6, a n d 8
a n d H.-R. S c h u l t e n , F a c h h o c h s c h u l e
F r e s e n i u s , W i e s b a d e n , F.R.G., who
carried o u t t h e m a s s s p e c t r o m e t r i c in-
vestigations.
References
(1) Lucas, A. "Ancient Egyptian Materials
and Industries," 3rd éd.; Arnold: Lon-
don, 1959; p. 548.
(2) Pliny. "Natural History"; Loeb Classi-
cal Library: London, 1952.
(,'i) Pliny. "Natural History," translation
of 4th Volume by H. Rackham; Harvard
University Press: Cambridge, Mass.,
1960.
(4) Hepper, F. N.; Reynolds, T. "Papyrus
and the Adhesive Properties of Rs Cell
Sap in Relation to Paper-making," J.
Egypt. Archeol. 1967, 53, 156.
(5) Ragab, H. "A New Theory Brought
Forward About the Adhesion of Papyrus
Strips," 14th International Congress of
Paper Historical, Manchester, 1978.
(6) Wiedemann, H. G.; Muller, V. G.;
Bayer, G. "Old Egyptian Papyrus Inves-
tigated by Thermogravimetrical Analy-
sis"; In "Proceedings of the Vth ICTA
Conference"; Kagaku Gijutsu-sha:
Japan, 1977; pp. 373-75.
(7) Wiedemann, H. G. "Paper technology
from Egyptian, Chinese, and Mayan cul-
tures," National Bureau of Standards
Special Publications 580; "Proceedings
of the Workshop on the State-of-the-Art
of Thermal Analysis"; NBS, Gaithers-
burg, Md., May 21-22, 1979 (issued May
1980).
(8) Basile, C. "A Method of Making Papy-
rus and Fixing and Preserving It by
Means of a Chemical Treatment"; In
"Conservation of Paintings and the
Graphic Arts"; Lisbon Congress 1972; In-
ternational Institute for Conservation of
Historic and Artistic Work: London,
1972; p. 901.
(9) Wiedemann, H. G. "Application of
Thermoanalytical Methods for Differen-
tiation between Ancient Papyri"; In
"Proceedings 4th Int. Conf. Surface and
Colloid Chemistry"; Jerusalem, July
1981, 1981, p. 122.
(10) Ebers, G. Papyrus Ebers; Verlag von
Wilhelm Engelmann: Leipzig, 1875.
(11) Banik, G. and Ponalho, I. "Some As-
pects Concerning Degradation Phenome-
na of Paper caused by Green Copper
Containing Pigments"; Int. Council of
Museums, 6th Annual Meeting, Ottawa,
1981.

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1230 A · ANALYTICAL CHEMISTRY, V O L 55, NO. 12, OCTOBER 1983