analytical techniques for manuscript

8/19/2019 Analytical Techniques for Manuscript

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Analytical techniques used for the evaluation of a 19th century

quranic manuscript conditions

Gomaa Abdel-Maksoud ⇑

Conservation Department, Faculty of Archaeology, Cairo University, Giza, Egypt

a r t i c l e i n f o

Article history:

Received 14 June 2010

Received in revised form 10 May 2011

Accepted 21 June 2011

Available online 29 June 2011

Keywords:

Paper

Leather

Microscopes

XRD

EDAX

Microorganisms

Chemical analysis

HPLC

a b s t r a c t

The manuscript studied here dates to 19th century, and consists of paper pages and leather

bookbinding. This study aims to use analytical techniques in order to identify the compo-

nents of the manuscript and to explain its deterioration process. Visual assessment, isola-

tion and identification of fungi, pH measurements, and investigation of the surface

morphology by a scanning electron microscope (SEM) were used to explain paper and

leather deterioration. X-ray diffraction with EDAX, Fourier Transform Infrared Spectros-

copy (FTIR), and chemical analysis were used to identify pigments, binder of pigments,

ash, lignin, and the a-cellulose content of papers. The shrinkage temperature measurement

was used to explain the deterioration process of leather. SEM was used to identify the type

of animal skin used for the bookbinding and high performance liquid chromatography

(HPLC) was used to identify the vegetable tanning material used with the bookbinding.

The results revealed that the ink used was a mixture of carbon with iron gall. The pig-

ments used on the paper were gold leaf or gold shell, cobalt oxide, and mercuric sulfide

for the gold, blue and red colors respectively. Sodium chloride was the main salt crystal-

lized on the surface of paper. Calcium carbonate was the filler used in the paper making

process. Cotton fibers may have been used as a raw material in the creation of paper.

The values of the shrinkage temperature and pH were lower than in normal conditions,

indicating that the leather bookbinding suffers from deterioration. Aspergillus sp., and

Penicillium sp. were the most dominant fungi found on the manuscript. Goat skin was

identified as the animal skin of the bookbinding, and Acacia Arabica was identified the

tanning material used with the bookbinding. The condition of the manuscript studied with

its components play an important role in its deterioration.

2011 Elsevier Ltd. All rights reserved.

1. Introduction

A major problem in the preservation of cultural heritageis the damage to manuscripts, mainly paper and bookbind-

ing. Damage can be caused by the effect of aggressive

atmospheres, humidity and temperature, alterations of

paper constituents, and added materials such as ink and

hand coloring with pigments or dyes [1]. Deterioration of

paper-based materials is mainly due to the degradation

of cellulose caused by a number of factors, such as chemi-

cal attack due to acidic hydrolysis, oxidative agents, light,

air pollution, and biological attack due to the presence of

microorganisms like bacteria and fungi [2,3].Leather products, such as the tanned skin of the book-

binding, have been useful materials since the dawn of

human history [4]. Vegetable tanned leather was used in

Egypt throughout the ages starting from the Prehistoric

Period [4] up until the present time [5,6]. Vegetable tanned

leather represents a very complex material composition.

The surroundings of the manuscript are likewise a very

complex and dynamic dimension, constantly varying with

respect to the quantity and degree of their interaction with

each other and with those materials stored within them

[7]. The most common types of damage sustained by a

0263-2241/$ - see front matter 2011 Elsevier Ltd. All rights reserved.doi:10.1016/j.measurement.2011.06.017

⇑ Tel.: +20 002 0184627960, 0193238347.

E-mail address: [email protected]

Measurement 44 (2011) 1606–1617

Contents lists available at ScienceDirect

Measurement

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e/ m e a s u r e m e n t

http://dx.doi.org/10.1016/j.measurement.2011.06.017mailto:[email protected]://dx.doi.org/10.1016/j.measurement.2011.06.017http://www.sciencedirect.com/science/journal/02632241http://www.elsevier.com/locate/measurementhttp://www.elsevier.com/locate/measurementhttp://www.sciencedirect.com/science/journal/02632241http://dx.doi.org/10.1016/j.measurement.2011.06.017mailto:[email protected]://dx.doi.org/10.1016/j.measurement.2011.06.017


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bookbinding are caused by poor handling, poor storage

methods, inappropriate display methods, wear and tear

from repeated use, chemical changes in the materials mak-

ing up the leather objects, chemical changes caused by

atmospheric pollutants and chemicals in contact with the

leather objects, and a combination of any or all of these

(http://archive.amol.org.au) [8].

Chemical deterioration of leather occurs through two

competitive and interactive chemical mechanisms,

oxidation and acidic hydrolysis [9]. Oxidation is generally

caused by free radicals generated by heating, UV light,

and SO2 and NO x pollution. The side chains of some amino

acids are initially involved, but oxidation can also occur in

the backbone of collagen through the rupture of N–C cova-

lent bonds [10]. Hydrolysis is catalyzed by both hydroxyl

and hydrogen ions, especially when atmospheric pollu-

tants such as SO2 and NO x act in conjunction with air

humidity, and cleavage of peptide bonds disrupts the

hierarchical structure of collagen [10]. Gelatinization, in

further denaturation and aggregation, leads to the irrevers-

ible formation of a heavily hydrated gel matrix. Partially

degraded collagen is especially susceptible to gelatiniza-

tion in warm, damp environments, since H-bonds are

exposed to the action of water [10].

The development of specific analytical techniques

improves the procedures to authenticate patrimonial ob-

jects made from collagen and cellulose-based materials

as well as the methods to study the impact of the environ-

mental factors. During the last few decades, many methods

of the analysis of paper and leather have been used for the

identification of the material compounds and for the esti-

mation of the deterioration processes. For paper, Ververis

et al. [11] used chemical analysis for the determination

of hemicelluloses, lignin, and ash content in paper. Strlič

et al. [12] mentioned that the measurement of the pH of

historical paper plays an important role to explain the

mechanism of deterioration. Many authors used different

analytical techniques for the identification of pigment used

on paper manuscripts [1,13,14]. FTIR was used for the

identification of ink binder [15,16]. For the leather book-

binding, the measurement of the shrinkage temperature

is vital and is considered one of the most important tools

used for the determination of leather deterioration [16–

21]. The measurement of leather pH reveals the state of

leather inside a museum or in storage [7,22]. Microbiolog-

ical studies and investigation of the surface morphology

are also very important for the estimation of the deteriora-

tion process for paper and leather [22–24].

This study aims to identify thematerialsused in theman-

uscript studied, apply the most effectiveness techniques of

analyses for the determination of paper and bookbinding

degradation, and explain the mechanism of deterioration.

2. Historical background

The manuscript was found in the library of Ahmed Al-

Bajam Mosque, located in Mehalit Marhoum Village, Tanta

City, Egypt. It was discovered during the destruction of the

mosque. It dates back to 19th century, and contains part of

the 28th chapter of the Holy Qur’an. It suffers from ground

and surrounding environmental damages, especially from

salts, such as sodium chloride.

3. Material and methods

For the determination of materials used with the man-

uscript and to explain the deterioration processes, all the

analytical techniques used in this study (pH, SEM, EDAX,

X-ray diffraction, FTIR, measurement of the shrinkage

temperature, HPLC and chemical analysis of paper) were

considered micro-destructive techniques because a few

micrograms are needed and can be collected from the loose

and separated fibers from the manuscript. The micro-

destructive techniques used were selected to obtain a sig-

nificant identification and to obtain the optimum amount

of information concerning the materials used. The analyti-

cal techniques used were more effective in explaining the

deterioration processes of the manuscript.

3.1. Visual assessment

Visual assessment, by the critical eye of the author, was

applied to determine the aspects of deterioration found on

the manuscript’s paper and leather. This method is very

effective because the causes and mechanism of deteriora-

tion may be easily identifiable. The critical eye of conserva-

tor can also determine the most effectiveness techniques of

analysis, which should be applied for identifying the condi-

tion of the manuscript studied.

3.2. Isolation and identification of fungi

Sterile swabs were used to wipe the surface of the paper

and the leather to isolate the fungi, especially in the

contaminated area. Isolation was made directly in the

laboratory after wiping process. The fungi were isolated by

wiping the swabs on culture medium of potato-dextrose-

agar (PDA) then incubated at 28 C for 1–2 weeks. Czapek

yeast extract agar (CYA) composed of K2HPO4 1 g, Czapek

concentrate 10 mL, yeast extract (Difco) 5 g, agar 15 g, dis-

tilled water 1 L [25]. The source of carbon (sucrose) was

not used andthe paperand leathersamples were thesource

of carbon. Seven-day cultures on Malt Extract Agar (MEA),

which consists of maltose 12.75 g, dextrin 2.75 g, glycerol

2.36 g, peptone 0.78, agar 15 g and distilled water 1 L, was

used for identification of isolated fungi [25]. Fungi colonies

were identified according to Raper and Fennell [26], Barnett

and Hunter [27], and Watanabe [28]. The balance used to

weight the components of media used for the isolation

and identification of fungi was calibrated using standard

weights traceable to SI (International Measurement Sys-

tem). All glass wares used here were calibrated and have

traceability to SI. Isolation and identification of fungi were

carried out at microbiological laboratories, the Department

of Microbiology, Krakow University of Agriculture, Poland.

3.3. pH measurement

3.3.1. Determination of leather bookbinding pH

The pH value of leather was determined by Abdel-Mak-

soud [22] in accordance with Wouters et al. [29] and the

G. Abdel-Maksoud / Measurement 44 (2011) 1606–1617 1607

http://archive.amol.org.au/http://archive.amol.org.au/


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National Library of the Netherlands [30] but with some

modifications. Samples (0.025 g) of leather bookbinding

is enough for the measurement and was taken mechani-

cally, in the form of loose fibers, from as near as possible

to the damaged area on the surface (grain) of the leather.

The sample was cut into very small pieces. The pH was

measured approximately 6 h after the suspension had been

prepared to allow the ions to migrate into the solution. The

measurement of pH value of the bookbinding was done

using a 315i InhaltsverzeTechnische Werkstatten GMBH

& Co. UG provided with a combination electrode and cali-

brated to between 2 and 7, at 21–22 C. The calibration

of pH meter was done by immersion of the pH electrode

firstly in distilled water and secondly into buffer solutions

(2 and 7). The model numbers of the technical buffers used

was 108,708 for the first buffer (pH 2) and 108,706 for the

second buffer (pH 7). After each measurement of the buf-

fers used, the pH electrode was rinsed in distilled water

followed by immersion in the buffer solutions. The calibra-

tion of pH meter was ok when the reading of pH meter was

stable and closed to the selected buffer value. The mea-

surement was performed in the Central Laboratory, Faculty

of Archaeology and Anthropology, Yarmouk University,

Jordon.

3.3.2. Determination of paper pH

The measurement of the pH of the paper was in accor-

dance with Strlic et al. [31] with little modification. A drop

of distilled water was placed on the paper of the manu-

script, the flat-surface combined pH electrode pressed

against it, and the pH value read after being constant for

30 s. The results are an average of five determinations.

The pH-meter Metrohm 691 (Metrohm, Herisau, Switzer-

land) was used with flat combined electrode (Metrohm

6,0253.100). Before the measurement of pH, the sensor

was calibrated using the provided buffer solutions accord-

ing to the instructions placed nearby the pH meter, pH

measurement was calibrated using three two standard

buffers (Metrohm buffers) of 4 and 7. The electrode with

immersed assembly in the first buffer and the temperature

measured was 25 C when the reading was stable and

closed to the selected buffer (pH 4), the measurement of

the first buffer was finished. The electrode was rinsed

again in distilled water. The pH electrode was rinsed into

the second buffer solution. When the reading of pH was

closed to the second buffer (pH 7), this means that the

pH meter was ready to measure the pH value of the histor-

ical paper samples. The measurement was performed at

the Organic Chemistry Laboratory, Department of Chemis-

try, Krakow University of Agriculture, Poland.

3.4. Investigation of the surface morphology by SEM and EDAX

analysis

A scanning electron microscope, JEOL-JSM-5400LV, was

used for the investigation of the surface morphology of the

paper and the leather. The fine gold coating (JEOL-JFC-

1100E) was used. All samples were photographed by SEM

at the Scanning Electron Microscope Laboratory, The central

Laboratory unit, Assiut University, Egypt. This laboratory

achieves the traceability via the manufacturer of the

instrument throughout the routine maintenance to achieve

best performance. For EDAX analysis, link ISIS Oxford was

used. The quantitative methodused wasZAF. Theresults ob-

tained from EDAX were automatically normalized to 100%.

EDAX was calibrated by the standard nickel rod purchased

along with the instrument. The Calibration was conducted

by count calibration mode in the software. EDAX were also

performed at the Scanning Electron Microscope Laboratory,

The central Laboratory unit, Assiut University, Egypt.

3.5. X-ray diffraction and EDAX analysis of ink and pigments

used

The ink samples of red, blue, and gold colors were

analyzed by X-ray diffraction using Compact X-ray Diffrac-

tometer System PW 1840 – Analytical Equipment – Philips

– Eindhoven – the Netherlands (CU Ka radiation with

Ni-filter). Calibration of X-ray diffraction was done by

using a silicon standard sample. The tube of copper was

used for the measurement. The mA and kV were adjusted.

The mA control was adjusted until the meter indicates at

50 mA. The kV was increased to 40. Two reflection angles

for the silicon standard should appear. One should appear

at 28.44 h and the other appears at 56.12 h. By this opera-

tion, the instrument was ready for the measurement. The

measurement was performed at the Laboratory of X-ray

diffraction analysis, Conservation Department, Faculty of

Archaeology, Cairo University, Egypt. Link ISIS Oxford

was used for EDAX analysis. The results obtained from

EDAX were automatically normalized to 100%. It should

be mentioned that all the decimal points obtained from

EDAX were effective. EDAX were performed at the Scan-

ning Electron Microscope Laboratory, The central Labora-

tory unit, Assiut University, Egypt.

3.6. Identification of pigment binder by FTIR

In order to identify the binder of the ink and pigments

used on paper of the manuscript, a few milligrams of the

ink and pigments taken from the manuscript was ground

into a powder and then mixed with KBr and placed in a

DRIFT cell. The measurement range is between 4000 and

400 cm1. The examination was done by using an infrared

instrument (Bruker) to identify the binder used with black

ink and pigments. Before measurement, the standard sam-

ple provided by the company of instrument is polystyrene

film. According to the instruction of the manufacturer, the

ideal measurement of this sheet must be placed in the

same position and intensity as the standard spectrum

saved at the library of the instrument. Before measurement

process, the background measurement was performed in

order to reduce the effect of the atmospheric carbon diox-

ide and water vapor. FTIR was performed at the Laboratory

of FTIR, Microanalysis Laboratory, Faculty of Science, Cairo

University, Egypt.

3.7. Measurement of hydrothermal stability of leather

bookbinding

This measurement was in accordance with Larsen [7]

but with little modification. A sample of about 0.3 mg fiber

1608 G. Abdel-Maksoud / Measurement 44 (2011) 1606–1617


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from the corium part of the leather was wet with distilled

water for at least 10 min on a microscope slide. Then the

samples were transferred to another slide with acetone

for at least 30 min and again transferred to distilled water

and glycerin. The fibers are separated, air bubbles were

removed with a needle, and the fibers were well dispersed

on the slide and secured. The microscope slide was placed

on the hot table. The gradient heat controller was cali-

brated at 22 C, as well as 80 C to achieve the traceability

to ITS 90 (International Temperature Scale). The timer was

calibrated using a calibrated stope watch traceable to

NIST–USA (National Institute for Standard and Technol-

ogy). The measurement of hydrothermal stability was

performed at the Analysis Laboratory, Animal Physiology

Department, Jagiellonian University, Poland.

3.8. Identification of animal skin used for the bookbinding

The surface examination by a scanning electron micro-

scope, JEOL-JSM-5400LV, was used to identify the type of

animal skin used for the leather bookbinding. A specimen

of about 2 mm 4 mm was aligned on a stub, with the hair

follicles opening towards the stub as viewed under the

microscope. The specimen was mounted on stub and

coated with fine gold. The nominal thickness of the sample

was 20 nm. The study of Haines [32] was taken as a refer-

ence in order to be compared with the identified skin from

the bookbinding studied. SEM was performed at the Scan-

ning Electron Microscope Laboratory, The central Labora-

tory unit, Assiut University, Egypt.

3.9. Identification of tanning material by High Performance

Liquid Chromatograpy (HPLC)

The samples and analytical procedure for High Perfor-

mance Liquid Chromatograpy (HPLC) were in accordance

with Wouters [33], and Abdel-Maksoud [34]. HPLC system

was calibrated for the flow rate using calibrated stopwatch

(traceable to standard cesium clock that has direct trace-

ability to SI measurement system at NIST–USA) and volu-

metric flask traceable to Si Measurement system. The

flow rate uncertainty was found 0.02%. Regarding the par-

ticle sizes, the system was calibrated using the standard

polystyrene dispersed particulates in aqueous system of

sizes 2 and 3 lm. Photometric scales was calibrated using

standard [0.1 N] potassium dichromate solution and the

total expanded uncertainty was found ±0.20% with cover-

age factor of two to give confidence level of 95%.

Samples were prepared from the bookbinding and from

Acacia Arabica, supplied by the Commercial Tannery, Cairo,

Egypt, and mimosa and quebracho powders, supplied by

Abd El-Rahman M. Harraz. Agricultural Seeds, Spices and

Medicinal Plants Company, Cairo, Egypt. A sample of dry

vegetable-tanned bookbinding weighing 50 mg was col-

lected from loose fibers around the bookbinding. 100 mg

of each of the new tanning powders was weighed and

soaked in a solution of water/acetone (1/1, v/v) in closed

vessels at room temperature for 24 h. The volume of the

extract liquid was 20 mL for 20 mg of acclimatized vegeta-

ble tanned bookbinding and tanning powder, weighed

after conditioning for at least 48 h at 65%RH and 20 C. Just

before chromatography, an aliquot of the water/acetone

extract was diluted fivefold with methyl alcohol. Extract

analyses were performed immediately. The results pre-

sented here are those recorded for the bookbinding and

Acacia Arabica powder because of their similarity. The

samples were analyzed using a Varian Pro Star, 3 lm,

100 6.4 mm column; pump (Varian Pro Star 230); 990+

photodiode-array detector (Varian Pro Star 335); data

handling using Star chromatography WS (work station)

version 6; 20 lL sample loop; flow rate: 1.2 mL/min; ana-

lytical wavelength 280 nm (other postrun selections possi-

ble between 200 and 800 nm); flow scheme (A = methanol,

B = water, C = 50 g/L phosphoric acid in water): 10A/80B/

10C for 2 min, linear gradient to 90A/10C over 17 min,

90A/10C for 3 min; temperature 21 C. The identification

of tanning was performed at the Analytical chemistry

Laboratory, the Department of Chemistry, Yarmouk

University, Jordan.

3.10. Chemical analysis of paper

3.10.1. Ash content

The ash was estimated by igniting in a muffle furnace a

weighed sample in a porcelain crucible for 30 min at

400 C, then continuously for 45 min at 850 C and then

gravimetrically estimated (Tappi standard 211-om 85)

[35]. The percentage of ash was calculated from:

Ash% ¼ Weight of ashðafter ignitionÞ

Weight of dry paper sampleðbefore ignitionÞ

100

Muffle furnace was calibrated at 400 C, 850 C and

1000 C using calibrated thermocouple that has traceabil-

ity ITS 90 (International Temperature Scale). Ash contentwas determined at the Cellulose Laboratory, Department

of Cellulose and Paper, National Research Center (NRC),

Egypt.

3.10.2. Lignin

An exact weight of 1 g of the air-dried sample was

treated with 15 mL of 72% sulfuric acid for 2 h at room

temperature. The material was then transferred into a 1 L

flask, diluted with 560 mL of distilled water, and boiled un-

der reflux for 4 h. The lignin was filtered on a previously

weighed dry ashless filter paper, and then washed with

hot distilled water till neutrality. The filter paper and lignin

were transferred to a weighted porcelain crucible and

dried in an oven at 105 C (The drying oven was calibrated

at 105 using calibrated glass thermometer traceable to ITS

90) till constant weight.

For ash correction, the contents of the crucible were

ignited at 400 C for 30 min and then at 850 C for further

45 min. The weight of the ash was subtracted to give the

weight of the pure lignin. Lignin percent is calculated from:

Lignin% ¼weight of lignin Weight of its ash

Weight of moisture free pulp 100

Determination of lignin was performed at the Cellulose

Laboratory, Department of Cellulose and Paper, National

Research Center (NRC), Egypt.


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3.10.3. a-cellulose content

25 mL of 17.5% sodium hydroxide solution was added to

3 g, exactly weighed, and cut into small pieces. The slurry

after being left to swell for 4 min, time exactly measured

from the last drop, at 20 C, was pressed for 3 min, with

glass rod, and 25 mL 17.5% sodium hydroxide solution

were added. The suspension was thoroughly mixed for

about 1 min and left covered at 20 C. After 35 min,

100 mL of distilled water was added followed by filtration

in a sintered crucible. The filtrate was poured twice on the

paste before washing with distilled water untill complete

neutrality and then with 10% acetic acid followed by dis-

tilled water. The temperature must be kept constant at

20 C during the whole experiment. The a-cellulose was

estimated gravimetrically after dryness in drying oven at

105 C for 6 h. The percent of a-cellulose is calculated as

follow:

% a-cellulose ¼B

A 100

where A represents the weight of dry sample, and B is theweight of dry treated samples.

All glass wares used for the determination of a-cellu-

lose content a-cellulose content were calibrated and have

traceability to the Egyptian National kilogram number

58. Determination of a-cellulose was performed at the Cel-

lulose Laboratory, Department of Cellulose and Paper, Na-

tional Research Center (NRC), Egypt.

4. Results and discussion

4.1. Visual assessment

The storage of the Qur’an manuscript was very poor andled to advanced deterioration. The following aspects of

deterioration were noticed on the leather bookbinding

(Fig. 1A and C): folding of the fibers in some places, white

hard crust may be from storage, general hardness, fungal

spots, erosion of tanning material, holes caused by insects,

and missing parts. The following aspects of deterioration

were noticed on the papers of the manuscript (Fig. 1B

and D): dog-earred pages, local damage at the corners with

multiple folds and creases, turning over of the paper so

that the front or back surface is in contact with itself, local

missing parts at the corners with multiple folds and

creases, stains derived from different sources (fungi, fats,

dusts, ink and pigments) and improper restoration, totaldestruction of paper edges and sometimes turned to pow-

der, and salt crystallization on the surface of paper and led

to erode the papers.

4.2. Identification of fungi

The results of this study revealed that the most domi-

nant fungi on papers of the manuscript were: Penicillium

restrictum, Penicillium spinulosum, Penicillium rubrum, Peni-

cillium chrysogenum, Aspergillus fumigates, Aspergillus niger,

Aspergillus flavus, Aspergillus ustus, Aspergillus terreus, and

Chaetomium sp. The most dominant fungi found on leather

bookbinding were Penicillium oxalicum, P. rubrum, Penicil-

lium funiculosum, A. fumigates, A. niger, A. flavus, Aspergillus

versicolor, Aspergillus Wentii, and Fusarium sp.

Leather and paper are organic materials and are suscep-

tible to numerous biodeterioration processes, which

generally cause the loss of aesthetic properties and often

the irreversible degradation of important documents and

works of art [36]. The identified fungi are common on

historical papers and most of them are considered decom-

posed fungi for cellulosic and protein materials like paper

and leather [36]. Kowalik [37] and Held et al. [38] reported

that the bideterioration of cellulosic and proteineous mate-

rials by fungi depends mainly on the chemical composition

of the materials, its pH, its moisture content and the rela-

tive humidity of the environment, and the temperature

and the illumination. According to the promoting factors

mentioned above by Kowalik, Abdel-Maksoud [39] re-

ported that the conditions in most historical places in

Egypt are out of international standards that should be ap-

plied in museums, storehouses and libraries. It was found

by the measurement of pH (see below) of the manuscript

that the pH of paper and leather were acidic and fungi

prefer this level of pH. Some other factors encouraged

mold growth, such as a rapid fluctuation in relative

humidity associated with high changes in day and night

temperature.

4.3. pH measurement

It was noticed that the pH of leather was acidic, but the

acidity decreased more than the level in the normal state of

pH (3–5 pH). The pH of the leather bookbinding ranged be-

tween 2.5 and 2.9. The reduction of pH may be due to acid

accumulation in the leather, caused either by insufficient

removal of acidic residues from processing or by air-pollu-

tion, which can reduce the pH of the leather to fall below

3.0. Originally the effect of acid on leather is a general soft-

ening of the latter. After prolonged exposure, however, this

softening is transformed into a mellowness of the grain

and the leather structure become brittle. The next stage

is decay and total disintegration. The action of acids is

more destructive on vegetable-tanned leather [40].

The results of paper pH measurements showed that all

the paper studied showed acidic levels. The pH of studied

papers were 6.5, 5.6, 4.1 and 5.2 for original paper used

for writing, paper used in the restoration process, interior

lining paper and exterior lining paper, respectively. The re-

sults revealed that although the original paper was from

cotton fibers (as it will be explained later by SEM and

chemical analysis), the pH was acidic. This may be due to

some acids that formed within the papers, or those ab-

sorbed from the environment that were neutralized before

they had a chance to degrade the cellulose chains [41]. It

was stated that fibers made of cellulose chains degrade

when exposed to an acidic environment in the presence

of moisture. In this acid hydrolysis reaction, cellulose

chains are repeatedly split into smaller fragments so long

as the source of acid remains in paper. This acid hydrolysis

reaction produces more acid in the process, and the degra-

dation accelerates [41]. The results also revealed that the

interior lining paper had high acidity (4.1 pH). This may

be due to the internal factors such as the paper making



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process, and external factors such as environmental

conditions.

In the paper making process, especially in the late 19th

century, paper deterioration was further hastened by the

introduction of mechanically produced ground wood pulp.

These products, frequently not chemically purified, re-

sulted in weaker paper and the additional formation of

acids and peroxides that promote the aging process. The

paper made of ground wood pulp contained lignin, which

degrades to form acids and peroxides that further promote

the aging process. It can be added that the using of alum-

rosin sizing, especially in the mid 19th century onward,

causes the paper to eat itself from the inside out. In reac-

tion with the natural residual moisture in paper, alum

gradually breaks down to sulfuric acid, which attacks the

long chains of cellulose, breaking them into shorter and

shorter fragments. The paper steadily weakens until it fi-

nally becomes so brittle that it is unusable [41,42].

The external factors contain a series of chemical ele-

ments such as oxygen, nitrogen, ozone, and carbon dioxide.

These elements are responsible for the combustion,

fermentation, hydrolysis, and the oxidation of books and

documents. The atmosphere, especially of industrialized

zones, also contains a series of impurities, the results of

pollution or contamination, such as carbon dioxide, nitro-

gen dioxide, and sulfur dioxide. By-products of industrial

combustion which, catalyzed by metals, react with water

to form acids. The most important of these is sulfuric acid,

which leads to total weakness in the paper [42].

4.4. Investigation of the surface morphology by SEM and EDAX

analysis

Investigation of the paper by a SEM showed that fibers

of the original paper (Fig. 2A) seem to be from cotton.

Small amounts of filler materials appeared between the fi-

ber structures. Some contaminations (Fig. 2B) from stains

and dusts were noticed on the surface of the original paper.

Damages caused by insects (Fig. 2C) appeared in the form

of bores, and the tearing of paper fibers and deformation

Fig. 1. Aspects of deterioration found on Qur’an manuscript: (1A and 1C) aspects of deterioration of a bookbinding, (1B and 1D) aspects of deterioration of

papers.



7/12

of the paper appearance was also noted. The restoration

paper (Fig. 2D) displayed advanced deterioration. Many

forms of deterioration such as dust, stains, and the random

distribution and destruction of the fibers were recorded.

For the exterior lining paper (Fig. 2E) dust and stains cov-

ered the surface of paper and the fiber structures is unrec-

ognizable. The amount of filler materials seems to be

greater than in the original paper. For the interior lining

paper (Fig. 2F) accumulated dust and large amounts of fil-ler materials were noted.

Investigation of leather bookbinding (Fig. 3) showed the

destruction and random distribution of the fiber struc-

tures, erosion of the fibers, and many bores. There was to-

tal deformation of the surface morphology.

The results obtained by EDAX analysis of stains found

on leather bookbinding supported the fact that the manu-

script was found under the ground of the destroyed mos-

que, and this was reflected by the elements present on

the surface of leather. Calcium was found in the high per-

centage of 27.77%. Magnesium, aluminum potassium, and

silicon were also found, and this may indicate that the

ground consisted of lime with traces of clay minerals and

sand. Sulfur may act as a contaminant from the surround-

ing environment or from the manufacturing process of

leather bookbinding. Sodium also was found and may have

derived from the burial environment of the manuscript.

The sodium was further identified as sodium chlorideand it was found on all of the paper pages of the manu-

script. This type of salt led to the erosion of the surface

of both the papers and leather. The source of sodium chlo-

ride in the case study may be from saline in the soil and

groundwater, air pollution, and human contaminants. Salt

damage takes place when evaporation takes place, leaving

the salt to grow as crystals within the pores of the leather

or paper. The growth pressure of developing crystals is

very high and sufficient to cause erosion on the leather

Fig. 2. Investigation of deteriorated of paper by SEM: (A) original paper manuscript; (B) original paper with some stains and dusts; (C) original paper with

damaged caused by insects; (D) restoration paper; (E) exterior lining paper; (F) interior lining paper.

Fig. 3. Investigation of the surface morphology of leather bookbinding by SEM and analysis of stain found on the leather surface by EDAX.



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or paper sheets. The final result is total deformation of the

surface.

4.5. X-ray diffraction and EDAX analysis of ink and pigments

used

4.5.1. Gold color

It was clear from X-ray diffraction (Fig. 4A) and EDAX(Table 1) that the gold color was from gold leaf or gold

shell. Gold leaf was applied before any painting was done

because it would stick to the medium used to suspend

the paints. Shell gold was also used to illuminate manu-

scripts, it is made of powdered gold suspended with

gum. It was cheaper than gold leaf and could be applied

with a pen or brush. Shell gold allowed for finer detail

and could be applied after the paint.

4.5.2. Red color

The data obtained (Fig. 4B and Table 1) showed that the

red color, Vermillion, was formed from red mercuric sul-

fide obtained from cinnabar, the principle ore of mercury,or artificially by heating sulfur and mercury together [43].

4.5.3. Blue color

It was clear from Fig. 4C and Table 1 that the blue color

consisted mainly of cobalt oxide with aluminum oxide. Co-

balt blue was useful in all techniques, as well as being

lightproof. It needed a binder like gum Arabic [43]. Sodium

chloride was also identified, and was found with paper

support of the manuscript.

4.5.4. Black ink

Iron gall ink is the most important ink used in old

manuscripts. Many recipes exist for manufacturing black

ink (Fig. 4D), and usually contained a mixture of carbonand iron gall. Therefore a wide range of different compo-

nents and impurities exist for historical inks. The results

from the analysis of black ink showed the use of iron and

sulfur (iron sulfate), as seen in Table 1. In this study the

ink used may be a mixture of carbon and iron gall ink.

The significant amount of calcium, potassium, and magne-

sium in the black ink samples demonstrates the possible

use of gum Arabic as a binding media [13].

4.6. Identification of pigment binder by FTIR

The binder used with the black ink and pigments (Fig. 5)

was identified as gum Arabic after a comparison with thecontrol sample of pure gum Arabic. Bands at 2965–

2880 cm1 and 1415–1380 cm1 are assigned to CH3 and

CH2, which by its chemical composition is similar to natu-

ral hydrocarbons such as gum Arabic. A very strong band at

1030 cm1, due to C–O, indicated the characteristics of

polysaccharides. The identified gum Arabic also contained

Fig. 4. X-ray diffraction pattern of ink and pigments used on the paper of the manuscript.



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moderately strong bands at 1625–1630 cm1. Derrick et al.

[44] explained that bands at 1625–1630 cm1 is partially

associated with intramolecularly bound water and par-

tially due to the presence of a carboxyl group.

4.7. Measurement of hydrothermal stability of leather

bookbinding

The hydrothermal stability of collagen fibers, shrinkage

by heating in water, is a particularly good measure of the

strength or quality of leather and skin materials and the

degree of their deterioration [7]. Raw collagen, when

heated in water, shrinks at about 65 C [45]. Chemical

cross-links introduced into the collagen by tanning agents

raise the shrinking temperature depending on the type of

tanning material and the nature of the process employed

[46]. The shrinkage temperature of vegetable tanned

leather is between 75 and 85 C [46]. Larsen et al. [17] re-

ported that the phrase ‘shrinkage activity’ is used to denote

any observable shrinkage process going on in a fiber, thin

or thick, and the phrase ‘intensity of the shrinkage activity’

as a qualitative measure of the number of the observable

shrinkage processes taking place at a small temperature

interval.

The results (Fig. 6) revealed that the average five mea-

surements of the shrinkage temperature of the historical

leather bookbinding sample was 64 C. The shrinkage tem-

perature of the historical leather decreased from 15 C to

25 C compared with the control samples. Haines [47] ex-

plained that the reason for the shrinkage temperature is

that the backbone chains of the molecule exist in an ex-

tended form, held in this form by hydrogen bonding. Whencollagen is heated there is a point where the energy input

exceeds that of the hydrogen bonding. Then there is a sud-

den release from the extended form and the fibers shrink

to a rubber-like consistency. Only the remaining covalent

and salt bonds hold the collagen molecules together and

prevent the shrunken collagen from immediately going

into solution.

The decreased shrinkage temperature in the historical

leather bookbinding may be due to ageing conditions.

Haines [46] reported that ageing conditions that bring

about hydrolytic or oxidative degradation of the collagen

cause breaks in the backbone chain of the molecule and

changes to the chemical composition of the side chains.These both lead to a reduction in the shrinkage

temperature.

Chahine [20] said that there are different factors that

influence the shrinkage temperature. They can be classified

into biological and non-biological factors. Biological factors

relate to the nature of animal species, its living conditions,

environment, age of the animal, and from where on the

body the sample was taken. Furthermore, it was shown

by different authors that the shrinkage temperature (Ts)

is related to the amino acid content of collagen, their posi-

tion in the chain, and their hydroxylation. Fish skin, for

example, has a lower content of amino acids and a lower

Ts than mammal skin. Non-biological factors include thenature of the heating medium, ionic environment, salts,

tanning, and ageing.

4.8. Identification of animal skin used for the bookbinding

It was clear by a study of the grain surface of the book-

binding by SEM and the comparison with the study of

Haines [32] (Fig. 7A and B) that the type of skin used for

the bookbinding was goat skin. The leather surface was

smoothed and glazed. The coarse follicles were in the form

of groups. There was a wide and smooth surface between

these groups. The grouping of coarse and fine follicles

was easily recognized.

Table 1

EDAX analysis of ink and colorants used on paper manuscript.

Color Elements (wt%) Total

Na Mg Al Si P S Cl K Ca Ti Fe Cu Zn Hg Au O Co

Gold 1.37 0.22 0.43 0.58 4.15 0.27 0.15 0.60 0.88 – 0.28 1.32 1.24 – 71.17 17.33 – 100

Blue 9.20 – 9.79 18.93 0.71 4.43 1.54 2.12 7.66 – 0.78 – – – – 42.63 2.22 100

Red 0.80 3.03 3.65 10.67 – 6.02 3.15 2.05 19.37 – 0.73 0.78 0.30 28.50 – 20.95 – 100

Black 2.65 2.45 3.24 11.32 1.19 4.59 9.35 4.09 18.40 0.33 3.82 0.82 0.62 – 37.12 100

Fig. 5. FTIR analysis of gum Arabic binder used with ink and pigments:

(1) control, (2) gold color, (3) red color, (4) black ink, and (5) blue color.



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4.9. Identification of tanning material by High Performance

Liquid Chromatography (HPLC)

The identification of the tannin type used with the book-

binding was determined by the comparison of the retention

times and UV spectra between Acacia Arabica powder and

tannin material extracted from leather bookbinding. It

was clear from the data obtained (Fig. 8A and B) that there

was a close similarity in the retention times for the effective

peaks of tanning extracted from the bookbinding studied

and the tanning extracted from Acacia Arabica powder.

The close similarity in the retention times ranged from be-

tween 1.727 and 4.454 min. The results proved that there

was a similarity in the spectral characterization of individ-

ual tanning peaks. The retention times (min) of the effective

peaks of Acacia Arabica powder (Fig. 8A) were 1.918, 2.268,

2.623, 3.820 and 4.454, respectively, and the UV spectra of

these peaks were 235.20 nm, 257.53 nm, 292.15 nm,

369.85 nm and 456.20 nm, respectively. The retention

times (min) of the effective peaks of the extracted tannin

from the leather bookbinding (Fig. 8B) were 1.727, 2.270,

2.670, 3.804 and 4.330 min, respectively, and the UV spec-

tra of these peaks were 230.10 nm, 260.45 nm, 296.65 nm,

365.28 nm and 450.20 nm, respectively. It should be noted

that most of the intensity of the tanning material extracted

from Acacia Arabica powder was higher than tanning mate-

rial extracted from vegetable-tanned leather bookbinding.

The clarity and high intensity of peaks of thespectra for Aca-

cia Arabica powder compared to those for the vegetable-

tanned leather bookbinding may have been due to the

mechanism of deterioration, oxidation or hydrolysis pro-

cesses, of the vegetable-tanned leather bookbinding. This

comparison clearly shows that the tanning material used

on the bookbinding has some similarity to Acacia Arabica.

Fig. 6. Microscopic pictures of vegetable tanned leather bookbinding: (A) shrinkage temperature of the sample at room temperature at 22 C, beforeshrinkage; (B) shrinkage activity of individual fibers at 48 C; (C) shrinkage activity in more than one fiber at 55 C; (D) shrinkage activity in some fibers at

59 C; (E) the final shrinkage activity at 64 C; (F) shrinkage temperature measurement of different sample of the leather bookbinding.

Fig. 7. Identification of animal skin: (A) goat skin (after Haines, 1981), (B) goat skin from the historical bookbinding.



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4.10. Chemical analysis of paper

The results of the chemical analyses for ash, lignin anda-cellulose are presented in Table 2. A high percentage

was recorded for a-cellulose in the original paper (57%)

and a low percentage was obtained from interior lining

paper (25%). For lignin and ash, a low percentage was

recorded with the original paper and the high percentage

was obtained from the interior lining paper. The paper

used in the restoration process contained higher percent-

age of lignin and ash than the original paper, but these per-

centages were lower than the interior and exterior papers.

These results argue that pure cellulose was used in the

manufacturing of the original paper and wood fibers may

have been used in the other papers. Due to the high cellu-

lose content and low lignin and ash contents of the originalpaper, it was relatively more resistant to the surrounding

environmental conditions than the other papers. Ververis

et al. [47] reported that paper made of wood fiber pulp is

weak and its resistance towards the surrounding environ-

mental conditions is poor.

5. Conclusion

This study proved that the manuscript studied suffers

from deterioration caused by surrounding environmental

conditions. By visual assessment and by investigation the

surface morphology (SEM), many aspects of deterioration

were noted on the surface of the papers or leather book-

binding, such as crystallization of the sodium chloride,

holes caused by insects, wrapping, erosion of tanning

material, and missing parts. The surrounding environmen-

tal conditions with the materials used in the manufactur-

ing of this manuscript play an important role in the

growth of fungi. The most dominant fungi were Aspergillus

sp., Penicillium sp., Chaetomium sp., and Fusarium sp. The pH

value of the paper and leather bookbinding were lower

than their values in the normal condition. This may due

to the manufacturing process and the surrounding

environmental conditions. The shrinkage temperature of

leather bookbinding was reduced compared to normal

the values of the shrinkage temperature of vegetable-

tanned leather. The reduction of the pH value of the leather

bookbinding below 3 pH may play an important role in the

reduction of the shrinkage temperature. The shrinkage

temperature of leather, gave a clear indication that the

manuscript suffers from deterioration. It proved that the

deterioration mechanism by hydrolysis or oxidation pro-

cesses caused breaks in the backbone chain of the molecule

and changed the chemical composition of the side chains.

The black ink was a mixture of carbon and iron gall. The

gold color was from gold leaf or gold shell, the red color

was from mercuric sulfide, and the blue color was from co-

balt oxide. The binder used with black ink and pigments

was gum Arabic. The scanning electron microscope inves-

tigation and chemical analysis of paper contents proved

that the original paper used as a support of writing mate-

rials was from cotton, but the wooden fibers may be used

in the exterior and interior papers used with the leather

bookbinding. Goat skin was the animal skin used for the

leather, and Acacia Arabica was the tanning material used

with the bookbinding studied.

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Fig. 8. HPLC elution profile: (A) New tanning material extracted from Acacia Arabica. (B) Tanning material extracted from vegetable-tanned bookbinding.

Table 2

Chemical analysis of paper.

Samples Components (%)

a-cellulose Lignin Ash

Original paper 57.0 0.8 1.3

Restoration paper 38.9 4.2 2.8

Interior lining paper 22.5 10.7 4.2

Exterior lining paper 35.9 6.8 3.4



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