Research ArticleDocumentation and Evaluation of an Ancient PaperManuscript with Leather Binding Using Spectrometric Methods

Rushdya Rabee Ali Hassan1 Mona F Ali1 Abdel-Gawaad A Fahmy2 HayssamM Ali 34

and Mohamed Z M Salem 5

1Conservation Department Faculty of Archaeology Cairo University 12613 Giza Egypt2Chemistry Department Faculty of Science Cairo University 12613 Giza Egypt3Botany and Microbiology Department College of Science King Saud University PO Box 2455 Riyadh 11451 Saudi Arabia4Timber Trees Research Department Sabahia Horticulture Research Station Horticulture Research InstituteAgriculture Research Center Alexandria Egypt5Forestry andWood Technology Department Faculty of Agriculture (El-Shatby) Alexandria University Alexandria 21545 Egypt

Correspondence should be addressed to Mohamed Z M Salem zidan_forestyahoocom

Received 19 March 2020 Accepted 2 June 2020 Published 24 June 2020

Academic Editor Claudia Crestini

Copyright copy 2020 Rushdya Rabee Ali Hassan et al )is is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in anymedium provided the original work isproperly cited

)e present study presented an integrated analytical approach to the Qurrsquoanic manuscript with leather binding the multianalysesrevealed the degree of degradation for paper and leather in the current manuscript under the study causing the mapping oftreatment )e visual assessment detected yellowness in the internal papers dark black spots and advanced erosion in the leatherbind)e result detected that this manuscript leads to yellowing and weakness in the properties of paper under the attack of aciditywhere the pH of paper reached 55 XRD and FTIR analyses of paper illustrated a dramatic decrease of crystallinity index with anotable increase of CO stretching respectively )e sharp increase of carbonyl group can be used as evidence of oxidation )emicroscopic examination also showed that cotton was used in the manufacturing of the paper of the current manuscript while theleather bind was made from goatskin In addition the cellulose and protein bundles were both destructive and disintegrated

1 Introduction

Manuscripts were the main preoccupation of those inter-ested in human heritage and history during human civili-zation Manuscripts contained the history of humankindfrom the earliest ages )e papyrus manuscripts appeared inancient Pharaonic civilization Ancient Egypt was a source ofpapyrus which was exporting it to the rest of the world )eEuropean civilization also introduced the use of animalleathers treated with alkali materials such as lime for theprocessing of so-called parchment which recorded the finestdecorative writings At the top of the cognitive pyramid ofmanuscripts and writings was paper pulp )e achievementis due to the Chinese who succeeded in converting vegetablefibers such as bamboo to an easy-to-write material calledldquopaperrdquo in 105 AD and some recent excavations conducted

by Chinese University in Hong Kong indicted that paper wasknown even before this day )e paper lingeringly movedthrough Chinese merchants to Arab countries such as IraqSyria and Egypt We find a number of Arabic manuscriptsbelonging to the 9th century written on paper [1 2] Euro-peans learnt the method of papermaking almost 500 yearsafter it was known in Samarkand One of the wonderful thingsin paper is that it is used from centuries to the present daySide to side there was the leather as an external cover [3ndash5]

Many of the studied manuscripts have dealt with paperand its composition which is not new but there is an urgentneed to explain the chemical composition of the paper andits chemical properties to understand the nature of thesubstance of the study

Cellulose is the main component of paper a normalpolymer of glucopyranose units (β-D) and these units are

HindawiJournal of ChemistryVolume 2020 Article ID 6847910 10 pageshttpsdoiorg10115520206847910

linked together by the association of β-glycosidic bond to befinally a long chain and are connected with other hydrogenbond chains which give strength to paper fibers [6]

)e cellulose molecules are arranged to be fine bundleswhich are eventually assembled to be fibers )ere are twosystems for arranging the paper molecules (i) areas withspecific crystalline patterns known as crystalline regionwhere cellulosic chains are formed parallel to each other and(ii) areas in which the fibrous are irregular and random oramorphous [7 8] )ese regions are longer than non-crystalline regions Cellulose is characterized by manyproperties but there are properties that are the focus of theattention of the conservator which explain how themechanism of damage and aging led to choose the possibletreatment and maintenance

Cellulose is somewhat amorphous so it has the X-raydiffraction characteristic )e advanced damage underdegrading factors can change the crystallization rate)erefore the method of ray diffraction can be used toidentify the crystallized areas in the paper In addition thecellulose is highly sensitive to strong alkaline solutions )epaper loses its strength It is converted to alkaline cellulosewhich easily dissolves into the less stable cellulose hydrates)is information is important for the reagent when handlingpaper with alkaline solutions such as deacidification or otheralkaline solutions during conservation Paper shall be in safeconditions of acidity [9 10]

Different analytical characterization techniques such asattenuated total reflectance Fourier transform infraredspectroscopy (ATR FTIR) and X-ray diffraction (XRD) wereused to elucidate the cellulosersquos main features to identify theinorganic composition of the papers and to study thecrystallinity of the samples [11ndash16]

Dilute acids dissolve the cellulose and the result is theless stable hydrocellulose of the chemical reactions )ecellulose formation shows hydrolysis with water release dueto the bonding between the OH group and the adjacenthydrogen atom )e degradation is also accompanied by theformation of aldehyde and carboxyl groups [17 18] Paper isa hygroscopic substance that absorbs water from the sur-rounding environment so the temperature and humiditysurrounding the paper manuscripts must be adjustedCellulose does not exist alone in the composition of paperbut there is a natural lignin which increases the rate ofcellulose decomposition especially in sunlight or industriallight which leads to yellowing of the paper due to the ab-sorption of harmful UV rays [19 20]

Despite many information on the process of the man-uscript industry the study of archaeological samples answersmany questions to both chemists and conservators ofmanuscripts Archaeological manuscripts are also exposedto various causes of damage such as atmospheric gaseswhere oxygen and water vapormake the atmosphere suitablefor relaxation and auto-oxidation [21ndash24]

Sulfur dioxide as an air pollution gas is absorbedthrough the surfaces of manuscripts and high-porous leatherand reacts with small quantities of metal compounds es-pecially iron which is attached to books manuscripts anddocuments in the form of dust )ere is no doubt that the

cycle of night and day as well as the succession of industriallighting tend to auto-oxidation and damage for the col-lection of books and manuscripts [25 26]

Heat also plays a vital role in the growth of microor-ganisms On the other hand heat accelerates the chemicaldamage of papyrus parchment and paper [27ndash29] In ad-dition adhesives used to bind books and manuscripts suchas glue and flour paste lose the strength of the heat paste Inorder to understand the nature of the materials involved inthe making of manuscripts and leather covers and to de-termine the current state of damage accurately there mustbe an effective analytical strategy based on modern methodsand methods in the field of study of manuscripts which ispresented by the current research paper using several an-alytical methods

2 Materials and Methods

21 Description of the Manuscript A Qurrsquoanic manuscriptdating back to the Ottoman periodmdashthe tenth centuryAHmdashwas selected from the confines of the library of Al-Azhar Al-Sharif based on the degree of deteriorations )efollowing archaeological manuscript was used in the presentstudy the Qurrsquoanic manuscript (the third quarter of theHoly Quran) the special code for this manuscript is 838 andgeneral code is 88919

)e Qurrsquoanic manuscript includes 28 sheets written incarbon ink with a leather cover in dark brown color with anumber of geometric decorations located in the center of thelashes of the front of the manuscript In addition to geo-metric decoration on the four sides in the form of rectanglesintertwined within them a vegetal motif adorns the foursides )e decoration is applied in a pressurized manner onthe leather and its inner writings are framed )e stateengineering registration and characterization of the man-ifestations of damage before the restoration methods weredescribed [30 31]

22 Documentation by Visual Assessment and PhotographyA Qurrsquoanic manuscript from Turks Gallery at the libraryof Al-Azhar Cairo which is part of the group ldquoOsmanKtekhdardquo as written on the first page of the manuscriptwas analyzed )e dimension of the manuscript is148 cm times 208 cm

23Measurement of the pH )e pH measurements of paperand the leather were performed using ML1010PH (MisuraLine Romania) with the method of cold extraction where1 g sample of each of leather or paper was soaked in 70mL ofwater for 1 h [32] as described in previous work [30])e pHmeter with a combination electrode was calibrated betweenpH 3 and 7 at 28degC

24 Scanning Electron Microscopy (SEM) )e manuscriptsuffered a number of damage due to the poor storageconditions in warehouses that are not equipped with themeans of controlling the temperature humidity and light

2 Journal of Chemistry

which were revealed through the previous stages of docu-mentation Scanning electron microscopy was used forleather and paper of the manuscript to identify the internaldamage of the leather and paper In addition a comparisonbetween the archaeological samples and modern samples ofleather and paper was undertaken to identify the type offibers

Specimens from leather and paper with size of 10mm indiameter circular shape were used for SEM examinations)ese samples were subjected to sputter coating (Edwardsrsquosmodel S 140A) of gold ions to have a conducting mediumSputter coated samples were scanned with JEOLModel JSM-T20 SEM

25 Cellulose Crystallinity Determination by X-Ray Diffrac-tion Analysis Crystallinity of cellulose was determinedusing Compact X-ray Diffract meter System PW 1840Analytical Equipment (Philips Eindhoven the Netherlands)(CU Ka radiation with Ni filter) was used for determiningthe paper crystallinity )e degree of crystallization of cel-lulose (crystallinity index) was measured according to thefollowing equation [30 33]

ICrys I002 minus Iam

I0021113896 1113897 times 100 (1)

where ICrys crystallinity index I002 intensity at approxi-mately 2θ 226deg and Iam intensity at approximately2θ19deg

26 FTIR Spectroscopy Analysis )e IR spectra of sampleswere measured using Nicolet380 (FTIR) spectrometer withattenuation total reflection (ATR) mode having a zinc sel-enide crystal in the range of wavelength 650ndash4000 cmminus1)eIR absorbance frequencies for the samples under test wererecorded with an average of 128 scans using a resolution ofapproximately 4 cmminus1

3 Results and Discussion

31 Visual Assessment and Photography Figure 1 illustratesthe state of manuscript before the restoration process wherethe damage symptoms are visually seen From the figure thedeep erosion in the outer leather cover yellowness in theinternal papers and dark black spots on the edges of themanuscript paper were observed Furthermore erosion inthe outer cover and loss in different parts of the leather aswell as the mud smears are clearly shown on leather surface)ose phenomena of degradation indicate the bad condi-tions in which the manuscript was kept in addition to theeffects of heat air pollution and moisture on the paper andleather of the manuscript Some contaminations (Figure 1)from stains and dusts were noticed on the surface of theoriginal paper Damages caused by physical factors (such asheat and moisture) appeared in the form of bores and thetearing of paper fibers and deformation of the paper ap-pearance were also noted

Furthermore one of the most important types of doc-umentation and a means to measure the damage cracks and

insect holes of the manuscript is drawing and documenta-tion of the data using computer software (see Figure 2)where the fine cracks can be easily observed Some subtlecracks and color changes can only be detected using theseprograms which paints an integrated picture of the nature ofthe damage

32 SEM Examination of Deteriorated Manuscript SEMimages (Figures 3 and 4) showed a complete image of themost accurate details of internal damage on the level of fiberand the extent of the impact of various damage factors on theleather and paper and showed the extent of disintegrationand erosion in the internal leather fibers )e manuscriptcover was made from goatskin as was detected by com-parison with modern sample (Figure 3(a)) the fiber bundlesof goat usually are relatively fine and interweaved compactlyat a medium angle [31] )e fibers suffered from erosion andseparation and damage in the surface layer in addition to theerosion of fibers themselves (Figures 3(b)ndash3(e)) and thatsome bundles are completely destroyed

Figure 4 shows the SEM images of the manuscript paper)e image can confirm that paper is made from cotton rags(Figure 4(a)) )e paper contains some fillers such as calciterecovered from the calcite crystals (Figure 4(b)) Symptomsof erosion in paper fibers weakness and clear damage inmineral crystals of fillers are also shown (Figures 4(c)ndash4(e))In cultural heritage framework CaCO3 has been widely usedas a filler in ancient paper therefore the conservators used itfor the deacidification of paper damaged by the presence ofiron-gall inks or by interaction with the external environ-ment [34 35] Also Figure 4(e) shows mycelium and sporesof some species of fungi Deterioration may also be due tothe acids and enzymes produced as a metabolic activity ofmicroorganisms [36] At the same time fungi play a crucialeffect in the disintegration of stones and archaeologicalmaterials due to their enormous enzymatic activity [37]

33 pHof Leather andPaper )e pH of leather recorded wasabout 45 while it was 55 for paper)e results show that thepaper needs to be treated for acidity because the degree ofacidity of paper is ideally 70 and if it is lower than that as inthe manuscript it will lead to yellowing and weakness in theproperties of paper )e leather degree of acidity is some-what appropriate because the acidity of the leather must bewithin 40ndash60 but the leather can be treated also to providesome kind of future protection against acidity risk [15 38]

34 Crystallinity Index by XRD Analysis Fragments ofmanuscript paper were analyzed to detect the crystallinityindex the fragments were cleaned for any impurities or dustthat affects the results)e XRD peaks are shown in Figure 5)e paper is a semicrystalline cellulose fiber )erefore astudy of its crystallinity may lead to a more detailedknowledge of the degradation process XRD results showthat there are noticeable differences in the amorphous andcrystalline regions in the paper under effect of damagefactors cultural heritage objects are subject to the influence

Journal of Chemistry 3

of environmental parameters ie light temperature andmoisture which cause different structural changes on thematerials )e long-term exposure to variable conditions

changes the structure and properties of the materials As aresult of those the fibers become less amorphous [39] )edegree of crystallinity in native cellulose records about

(a) (b)

(c) (d)

(e) (f )

(g) (h)

Figure 1)e various damage aspects of the manuscript no 833 (a) Erosion in the outer cover and loss in different parts of the leather withdifferent mud smears on leather surface (b) Corrosion in the leather (c) Patches of soot scattered in the pages of the manuscript (d) )eobvious acidity on the heel of the manuscript and the color and yellowness in the internal papers (e) )e scars in the inner paper (f ) Darkblack spots on the edges of themanuscript paper appearing inmore than one place in the manuscript (g) Erosion in paper from the heel areaof the manuscript as indicated by the arrow in addition to the large erosion in the contact areas of the LT (h))e deep erosion in the leatherand paper lining and manuscript

4 Journal of Chemistry

60ndash90 according to the type of source of cellulose wherethe cotton cellulose reaches about 85 while this valuereduced in case of flax or wood As shown in Figure 5ICrys ((326 minus 0682)326) times 100 7900 and this resultreveals a dramatic decrease in ICrys for paper )erefore therigidity of cellulose fibers increases and their flexibilitydecreases with decreasing ratio of crystalline to amorphousregions

35 XRD for Ink A preliminary chemical test was under-taken to identify the ink type the test showed that the inkwas not affected by 5 solution of iron and potassiumcyanide with 1 hydrochloric acid which proves to becarbon ink A fraction of the paper containing ink residueswas analyzed using X-ray diffraction and showed that thecarbon ink is composed of graphite particles (Figure 6)

Loss Cracks Insect holes

Figure 2 Documentation of the leather cover of manuscript on photoshop

100microm

(a)

10microm

(b)

100microm

(c)

10microm

(d)

10microm

(e)

Figure 3 SEM images of leather binding (a) )e superficial appearance of the leather which is very similar to the surface of goat leather(b) Clear cracks in the surface of the leather (c) Corrosion and insect holes (d e) Erosion of the surface layer and weakness of the leatherfibers in general

Journal of Chemistry 5

10microm

(a)

5microm

(b)

50microm

(c)

10microm

(d)

5microm

(e)

Figure 4 SEM images of surface appearance of a sample of the inner manuscript paper (a) )e surface appearance of the paper whosefibers are near the pulp fibers of the cotton core (b) )e fillers in the paper approximating the shape of the calcite crystal (calcite in thepapermaking process) (c) )e shape of a cotton fiber and its distinctive cylindrical shape (d e) Erosion and weakness of paper fibers withdisintegration in fibers

2θ

Inte

nsity

(101

) pea

k at

2θ

= 14

8deg

(101

-) p

eak

at 2θ

= 16

3deg

(002

) pea

k at

2θ

= 22

6deg

500

400

300

200

100

00

10 20 30 40

Figure 5 X-ray diffractograms of paper

6 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

which were revealed through the previous stages of docu-mentation Scanning electron microscopy was used forleather and paper of the manuscript to identify the internaldamage of the leather and paper In addition a comparisonbetween the archaeological samples and modern samples ofleather and paper was undertaken to identify the type offibers

Specimens from leather and paper with size of 10mm indiameter circular shape were used for SEM examinations)ese samples were subjected to sputter coating (Edwardsrsquosmodel S 140A) of gold ions to have a conducting mediumSputter coated samples were scanned with JEOLModel JSM-T20 SEM

25 Cellulose Crystallinity Determination by X-Ray Diffrac-tion Analysis Crystallinity of cellulose was determinedusing Compact X-ray Diffract meter System PW 1840Analytical Equipment (Philips Eindhoven the Netherlands)(CU Ka radiation with Ni filter) was used for determiningthe paper crystallinity )e degree of crystallization of cel-lulose (crystallinity index) was measured according to thefollowing equation [30 33]

ICrys I002 minus Iam

I0021113896 1113897 times 100 (1)

where ICrys crystallinity index I002 intensity at approxi-mately 2θ 226deg and Iam intensity at approximately2θ19deg

26 FTIR Spectroscopy Analysis )e IR spectra of sampleswere measured using Nicolet380 (FTIR) spectrometer withattenuation total reflection (ATR) mode having a zinc sel-enide crystal in the range of wavelength 650ndash4000 cmminus1)eIR absorbance frequencies for the samples under test wererecorded with an average of 128 scans using a resolution ofapproximately 4 cmminus1

3 Results and Discussion

31 Visual Assessment and Photography Figure 1 illustratesthe state of manuscript before the restoration process wherethe damage symptoms are visually seen From the figure thedeep erosion in the outer leather cover yellowness in theinternal papers and dark black spots on the edges of themanuscript paper were observed Furthermore erosion inthe outer cover and loss in different parts of the leather aswell as the mud smears are clearly shown on leather surface)ose phenomena of degradation indicate the bad condi-tions in which the manuscript was kept in addition to theeffects of heat air pollution and moisture on the paper andleather of the manuscript Some contaminations (Figure 1)from stains and dusts were noticed on the surface of theoriginal paper Damages caused by physical factors (such asheat and moisture) appeared in the form of bores and thetearing of paper fibers and deformation of the paper ap-pearance were also noted

Furthermore one of the most important types of doc-umentation and a means to measure the damage cracks and

insect holes of the manuscript is drawing and documenta-tion of the data using computer software (see Figure 2)where the fine cracks can be easily observed Some subtlecracks and color changes can only be detected using theseprograms which paints an integrated picture of the nature ofthe damage

32 SEM Examination of Deteriorated Manuscript SEMimages (Figures 3 and 4) showed a complete image of themost accurate details of internal damage on the level of fiberand the extent of the impact of various damage factors on theleather and paper and showed the extent of disintegrationand erosion in the internal leather fibers )e manuscriptcover was made from goatskin as was detected by com-parison with modern sample (Figure 3(a)) the fiber bundlesof goat usually are relatively fine and interweaved compactlyat a medium angle [31] )e fibers suffered from erosion andseparation and damage in the surface layer in addition to theerosion of fibers themselves (Figures 3(b)ndash3(e)) and thatsome bundles are completely destroyed

Figure 4 shows the SEM images of the manuscript paper)e image can confirm that paper is made from cotton rags(Figure 4(a)) )e paper contains some fillers such as calciterecovered from the calcite crystals (Figure 4(b)) Symptomsof erosion in paper fibers weakness and clear damage inmineral crystals of fillers are also shown (Figures 4(c)ndash4(e))In cultural heritage framework CaCO3 has been widely usedas a filler in ancient paper therefore the conservators used itfor the deacidification of paper damaged by the presence ofiron-gall inks or by interaction with the external environ-ment [34 35] Also Figure 4(e) shows mycelium and sporesof some species of fungi Deterioration may also be due tothe acids and enzymes produced as a metabolic activity ofmicroorganisms [36] At the same time fungi play a crucialeffect in the disintegration of stones and archaeologicalmaterials due to their enormous enzymatic activity [37]

33 pHof Leather andPaper )e pH of leather recorded wasabout 45 while it was 55 for paper)e results show that thepaper needs to be treated for acidity because the degree ofacidity of paper is ideally 70 and if it is lower than that as inthe manuscript it will lead to yellowing and weakness in theproperties of paper )e leather degree of acidity is some-what appropriate because the acidity of the leather must bewithin 40ndash60 but the leather can be treated also to providesome kind of future protection against acidity risk [15 38]

34 Crystallinity Index by XRD Analysis Fragments ofmanuscript paper were analyzed to detect the crystallinityindex the fragments were cleaned for any impurities or dustthat affects the results)e XRD peaks are shown in Figure 5)e paper is a semicrystalline cellulose fiber )erefore astudy of its crystallinity may lead to a more detailedknowledge of the degradation process XRD results showthat there are noticeable differences in the amorphous andcrystalline regions in the paper under effect of damagefactors cultural heritage objects are subject to the influence

Journal of Chemistry 3

of environmental parameters ie light temperature andmoisture which cause different structural changes on thematerials )e long-term exposure to variable conditions

changes the structure and properties of the materials As aresult of those the fibers become less amorphous [39] )edegree of crystallinity in native cellulose records about

(a) (b)

(c) (d)

(e) (f )

(g) (h)

Figure 1)e various damage aspects of the manuscript no 833 (a) Erosion in the outer cover and loss in different parts of the leather withdifferent mud smears on leather surface (b) Corrosion in the leather (c) Patches of soot scattered in the pages of the manuscript (d) )eobvious acidity on the heel of the manuscript and the color and yellowness in the internal papers (e) )e scars in the inner paper (f ) Darkblack spots on the edges of themanuscript paper appearing inmore than one place in the manuscript (g) Erosion in paper from the heel areaof the manuscript as indicated by the arrow in addition to the large erosion in the contact areas of the LT (h))e deep erosion in the leatherand paper lining and manuscript

4 Journal of Chemistry

60ndash90 according to the type of source of cellulose wherethe cotton cellulose reaches about 85 while this valuereduced in case of flax or wood As shown in Figure 5ICrys ((326 minus 0682)326) times 100 7900 and this resultreveals a dramatic decrease in ICrys for paper )erefore therigidity of cellulose fibers increases and their flexibilitydecreases with decreasing ratio of crystalline to amorphousregions

35 XRD for Ink A preliminary chemical test was under-taken to identify the ink type the test showed that the inkwas not affected by 5 solution of iron and potassiumcyanide with 1 hydrochloric acid which proves to becarbon ink A fraction of the paper containing ink residueswas analyzed using X-ray diffraction and showed that thecarbon ink is composed of graphite particles (Figure 6)

Loss Cracks Insect holes

Figure 2 Documentation of the leather cover of manuscript on photoshop

100microm

(a)

10microm

(b)

100microm

(c)

10microm

(d)

10microm

(e)

Figure 3 SEM images of leather binding (a) )e superficial appearance of the leather which is very similar to the surface of goat leather(b) Clear cracks in the surface of the leather (c) Corrosion and insect holes (d e) Erosion of the surface layer and weakness of the leatherfibers in general

Journal of Chemistry 5

10microm

(a)

5microm

(b)

50microm

(c)

10microm

(d)

5microm

(e)

Figure 4 SEM images of surface appearance of a sample of the inner manuscript paper (a) )e surface appearance of the paper whosefibers are near the pulp fibers of the cotton core (b) )e fillers in the paper approximating the shape of the calcite crystal (calcite in thepapermaking process) (c) )e shape of a cotton fiber and its distinctive cylindrical shape (d e) Erosion and weakness of paper fibers withdisintegration in fibers

2θ

Inte

nsity

(101

) pea

k at

2θ

= 14

8deg

(101

-) p

eak

at 2θ

= 16

3deg

(002

) pea

k at

2θ

= 22

6deg

500

400

300

200

100

00

10 20 30 40

Figure 5 X-ray diffractograms of paper

6 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

of environmental parameters ie light temperature andmoisture which cause different structural changes on thematerials )e long-term exposure to variable conditions

changes the structure and properties of the materials As aresult of those the fibers become less amorphous [39] )edegree of crystallinity in native cellulose records about

(a) (b)

(c) (d)

(e) (f )

(g) (h)

Figure 1)e various damage aspects of the manuscript no 833 (a) Erosion in the outer cover and loss in different parts of the leather withdifferent mud smears on leather surface (b) Corrosion in the leather (c) Patches of soot scattered in the pages of the manuscript (d) )eobvious acidity on the heel of the manuscript and the color and yellowness in the internal papers (e) )e scars in the inner paper (f ) Darkblack spots on the edges of themanuscript paper appearing inmore than one place in the manuscript (g) Erosion in paper from the heel areaof the manuscript as indicated by the arrow in addition to the large erosion in the contact areas of the LT (h))e deep erosion in the leatherand paper lining and manuscript

4 Journal of Chemistry

60ndash90 according to the type of source of cellulose wherethe cotton cellulose reaches about 85 while this valuereduced in case of flax or wood As shown in Figure 5ICrys ((326 minus 0682)326) times 100 7900 and this resultreveals a dramatic decrease in ICrys for paper )erefore therigidity of cellulose fibers increases and their flexibilitydecreases with decreasing ratio of crystalline to amorphousregions

35 XRD for Ink A preliminary chemical test was under-taken to identify the ink type the test showed that the inkwas not affected by 5 solution of iron and potassiumcyanide with 1 hydrochloric acid which proves to becarbon ink A fraction of the paper containing ink residueswas analyzed using X-ray diffraction and showed that thecarbon ink is composed of graphite particles (Figure 6)

Loss Cracks Insect holes

Figure 2 Documentation of the leather cover of manuscript on photoshop

100microm

(a)

10microm

(b)

100microm

(c)

10microm

(d)

10microm

(e)

Figure 3 SEM images of leather binding (a) )e superficial appearance of the leather which is very similar to the surface of goat leather(b) Clear cracks in the surface of the leather (c) Corrosion and insect holes (d e) Erosion of the surface layer and weakness of the leatherfibers in general

Journal of Chemistry 5

10microm

(a)

5microm

(b)

50microm

(c)

10microm

(d)

5microm

(e)

Figure 4 SEM images of surface appearance of a sample of the inner manuscript paper (a) )e surface appearance of the paper whosefibers are near the pulp fibers of the cotton core (b) )e fillers in the paper approximating the shape of the calcite crystal (calcite in thepapermaking process) (c) )e shape of a cotton fiber and its distinctive cylindrical shape (d e) Erosion and weakness of paper fibers withdisintegration in fibers

2θ

Inte

nsity

(101

) pea

k at

2θ

= 14

8deg

(101

-) p

eak

at 2θ

= 16

3deg

(002

) pea

k at

2θ

= 22

6deg

500

400

300

200

100

00

10 20 30 40

Figure 5 X-ray diffractograms of paper

6 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

60ndash90 according to the type of source of cellulose wherethe cotton cellulose reaches about 85 while this valuereduced in case of flax or wood As shown in Figure 5ICrys ((326 minus 0682)326) times 100 7900 and this resultreveals a dramatic decrease in ICrys for paper )erefore therigidity of cellulose fibers increases and their flexibilitydecreases with decreasing ratio of crystalline to amorphousregions

35 XRD for Ink A preliminary chemical test was under-taken to identify the ink type the test showed that the inkwas not affected by 5 solution of iron and potassiumcyanide with 1 hydrochloric acid which proves to becarbon ink A fraction of the paper containing ink residueswas analyzed using X-ray diffraction and showed that thecarbon ink is composed of graphite particles (Figure 6)

Loss Cracks Insect holes

Figure 2 Documentation of the leather cover of manuscript on photoshop

100microm

(a)

10microm

(b)

100microm

(c)

10microm

(d)

10microm

(e)

Figure 3 SEM images of leather binding (a) )e superficial appearance of the leather which is very similar to the surface of goat leather(b) Clear cracks in the surface of the leather (c) Corrosion and insect holes (d e) Erosion of the surface layer and weakness of the leatherfibers in general

Journal of Chemistry 5

10microm

(a)

5microm

(b)

50microm

(c)

10microm

(d)

5microm

(e)

Figure 4 SEM images of surface appearance of a sample of the inner manuscript paper (a) )e surface appearance of the paper whosefibers are near the pulp fibers of the cotton core (b) )e fillers in the paper approximating the shape of the calcite crystal (calcite in thepapermaking process) (c) )e shape of a cotton fiber and its distinctive cylindrical shape (d e) Erosion and weakness of paper fibers withdisintegration in fibers

2θ

Inte

nsity

(101

) pea

k at

2θ

= 14

8deg

(101

-) p

eak

at 2θ

= 16

3deg

(002

) pea

k at

2θ

= 22

6deg

500

400

300

200

100

00

10 20 30 40

Figure 5 X-ray diffractograms of paper

6 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

10microm

(a)

5microm

(b)

50microm

(c)

10microm

(d)

5microm

(e)

Figure 4 SEM images of surface appearance of a sample of the inner manuscript paper (a) )e surface appearance of the paper whosefibers are near the pulp fibers of the cotton core (b) )e fillers in the paper approximating the shape of the calcite crystal (calcite in thepapermaking process) (c) )e shape of a cotton fiber and its distinctive cylindrical shape (d e) Erosion and weakness of paper fibers withdisintegration in fibers

2θ

Inte

nsity

(101

) pea

k at

2θ

= 14

8deg

(101

-) p

eak

at 2θ

= 16

3deg

(002

) pea

k at

2θ

= 22

6deg

500

400

300

200

100

00

10 20 30 40

Figure 5 X-ray diffractograms of paper

6 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

Figure 6 shows that the ink was a carbon ink (graphite)Previously the black pigment was almost exclusivelyidentified as carbon in the form of soot charcoal or boneblack [40ndash42] )e carbon ink has many advantages such asparticles do not fade over time even when exposed to lightchemicals or when bleached because carbon is chemicallystable but carbon ink has a tendency to smudge in humidenvironments and can fade

As the examination shows there are compounds thatgive important information about the manuscript includingcalcium carbonate (chalk) which is used as a filler whichhelps in weighting the paper and protects it from the effectsof acidity [43] Hematite impurities usually exist with fillers

and have been shown in a number of archaeological spec-imens that are analyzed [44]

36 FTIR Spectra of Paper and Leather Figure 7 shows theresults of paper analysis using FTIR )e analysis was usedfor the paper and leather sample of the manuscript toidentify the nature of the damage and compare their resultswith modern samples on the level of paper [45 46] Paper isalso characterized by a number of groups including hy-droxyl absorption group of CH2-OH stretching in area at3300ndash3400 cmminus1 [47 48] )ere is a large ethereal group ofC-O stretching group in the region of 1000ndash1300 cmminus1 while

2θ

Inte

nsity

CaCO

3

Fe2O

3

Graphite47

300

250

200

150

100

50

00 10 20 30 40 50 60

Figure 6 XRD pattern of ink confirmed that ink composed the graphite particles

tr

ansm

ittan

ce

OH stretchingC=O stretching

Control

S833

110

108

106

104

102

100

98

96

94

92

4000 3500 3000 2500 2000 1500 1000Wavenumber (cmndash1)

Figure 7 FTIR spectra pattern of the paper compared with a modern standard paper

Journal of Chemistry 7

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

a spectrum of the archaeological paper shows a change in thechemical composition of cellulose through an increase insome absorption areas of its characteristic groups and adecrease in other areas and formation of new groups [12 49]

)ere is a significant lack of hydroxyl absorption groupCH2-OH Stretching at wavelength 3400 cmminus1 )ere is also asignificant decrease in the C-O stretching group in the re-gion 1300-1200-1100 cmminus1 which disappeared sometimesAlso there is more than a strong carbonic absorption areaCO stretching at the region 1600ndash1575 cmminus1 which canprove that cellulose of paper suffers from oxidation [47]

)e leather was analyzed on a sample of the externalbinding and compared with a modern leather sample(Figure 8) )e changes in the functional groups werecharacterized by the protein and appeared clearly in thesamples of modern leather )is was not damaged as thestandard sample was characterized by the presence of anumber of functional groups of leather protein and the mostimportant was N-H stretching band at wavelength3200ndash3400 cmminus1 [15 37 50] C=O stretching band atwavelength 2800ndash3100 cmminus1 C-N-H bending band atwavelength 1500ndash1565 cmminus1 and C-H bending at wave-length 1300ndash1480 cmminus1 were found

)ere have been changes in these groups in the ar-chaeological sample where there has been a lack of ab-sorption of a large number of groups such as N-H stretchingband at a wavelength of 3404 cmminus1 C-N-H bending band ata wavelength of 1553 cmminus1 and C=O stretching band atwavelength 2930 cmminus1 )ese changes indicate the role ofdamage and the disappearance of bonds in the peptide chainand the occurrence of rupturing in the hydrogen bonds thatconnect the secondary structure of the leather Heat as adamage factor increases the movement of moleculesresulting in the increase of the absorption peak and shifted

to the right in the chart until it was completely disappearedbecause of breaking the bond [51]

4 Conclusions

In the present study different spectroscopic analyses wereused to investigate and characterize the archaeologicalmanuscript of a Qurrsquoanic manuscript dating back to theOttoman periodmdashthe tenth century AH Visual observationshowed various damage aspects of erosion found in thebookbinding leather of manuscript as well as inside thepapers of the manuscript SEM images of the manuscriptpaper showed the symptoms of erosion in paper fibersweakness and clear damage in the paper board )e XRDpeaks confirmed the sharp decrease in the crystallizationvalues of paper under effect of damage factors furthermorethe Arabian artists used calcite which was mixed with ironimpurities as a filler material for Arabic paper FTIR spectracharacterized the leather by the presence of a number offunctional groups of leather protein which were affectednotably under effect of damage

Data Availability

)e data used to support the findings of this study are in-cluded within the article

Conflicts of Interest

)e authors declare that they have no conflicts of interest

Acknowledgments

)is research was funded by King Saud University (RSP-2020123) Riyadh Saudi Arabia

tr

ansm

ittan

ce

S833

Control

110

100

80

60

5040000 30000 20000 10000 4000

2

2

1

1

3

3

4

4

55

66 7

7

8

8

1010

9

9

11

1213

Wavenumber (cmndash1)

Figure 8 FTIR spectra analysis of the leather of the manuscript compared to a standard leather sample

8 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

References

[1] B F Benz L LopezMestas and J Ramos de la Vega ldquoOrganicofferings paper and fibers from the Huitzilapa shaft tombJalisco Mexicordquo Ancient Mesoamerica vol 17 no 2pp 283ndash296 2006

[2] F Mahdavi ldquoPaper before print the history and impact ofpaper in the islamic world by Jonathan M Bloom (NewHaven Yale university press 2001) 270 pp $4500rdquo Journal ofInterdisciplinary History vol 34 no 1 pp 129-130 2003

[3] A Karpowicz ldquoAgeing and deterioration of proteinaceousmediardquo Studies in Conservation vol 26 no 4 pp 59-60 1981

[4] A V Persikov Y Xu and B Brodsky ldquoEquilibrium thermaltransitions of collagen model peptidesrdquo Protein Sciencevol 13 no 4 pp 893ndash902 2004

[5] R Newman and M Serpico ldquoAdhesive and bindersrdquo inAncient EgyptianMaterial sand Technology p 112 CambridgeUniverse Press Cambridge UK 2000

[6] R R A Hassan and W S Mohamed ldquo)e impact of methylmethacrylate hydroxyethyl methacrylate loaded with silvernanoparticles on mechanical properties of paperrdquo AppliedPhysics A vol 124 no 8 pp 124ndash551 2018

[7] D Fengel and W Wegenel Wood Chemistry UltrastructureReactions Walter De Gruyter Berlin China 1989

[8] C John Preservation of Paper and Textiles of Historical andArtistic American Chemical Society vol II p 29 Wash-ington DC USA 1981

[9] O Antoinettec Cellulose =e Structure Slowly Unravelsp 173 University of Wales Cardiff UK 1996

[10] A Aabloo A D French R-H Mikelsaar and A J PertsinldquoStudies of crystalline native celluloses using potential energycalculationsrdquo Cellulose vol 1 no 2 pp 161ndash168 1994

[11] R R A Hassan ldquoFourier transform infrared spectroscopy todetect thermal degradation of vegetable and chrome-tannedleatherrdquo Spectroscopy Letters vol 52 no 5 pp 288ndash296 2019

[12] L Hajji A Boukir J Assouik et al ldquoConservation ofMoroccan manuscript papers aged 150 200 and 800 yearsanalysis by infrared spectroscopy (ATR-FTIR) X-ray dif-fraction (XRD) and scanning electron microscopy energydispersive spectrometry (S E MndashEDS)rdquo Spectrochimica ActaPart A Molecular and Biomolecular Spectroscopy vol 136pp 1038ndash1046 2015

[13] S Pessanha M Manso and M L Carvalho ldquoApplication ofspectroscopic techniques to the study of illuminated manu-scripts a surveyrdquo Spectrochimica Acta Part B Atomic Spec-troscopy vol 71-72 pp 54ndash61 2012

[14] A Duran J L Perez-Rodriguez T Espejo M L FranqueloJ Castaing and P Walter ldquoCharacterization of illuminatedmanuscripts by laboratory-made portable XRD and micro-XRD Systemsrdquo Analytical and Bioanalytical Chemistryvol 395 no 7 pp 1997ndash2004 2009

[15] M Mansour R Hassan and M Salem ldquoCharacterization ofhistorical bookbinding leather by ftir sem-edx and investi-gation of fungal species isolated from the leatherrdquo EgyptianJournal of Archaeological and Restoration Studies vol 7 no 1pp 1ndash10 2017

[16] M F Ali M M A Mansour N M Badr andM Z M SalemldquoA study of biodeterioration and chromatic alterations ofpainted and gilded mummy cartonnage at the Saqqara mu-seum storeroom Egyptrdquo Archaeometry vol 60 no 4pp 845ndash858 2018

[17] D Klemm B Philipp T Heinze and U Heinze Compre-hensive Cellulose Chemistry Wiley VCH vol 1 p 47Weinheim Germany 1998

[18] C Y Liang and R H Marchessault ldquoInfrared spectra ofcrystalline polysaccharides II native celluloses in the regionfrom 640 to 1700 cmminus1rdquo Journal of Polymer Science vol 39no 135 pp 269ndash278 1959

[19] H A Krassig ldquoCellulose-structure accessibility and reactivityrdquoin Polymer Monographs 11 M B Huglin Ed Gordon andBreach Science Publishers Amsterdam Netherlands 1993

[20] S C Gilmour Paper Its Making Me Chanting and Usagepp 89-90 )e National Association of Paper MerchantsLondon UK 1956

[21] L Le ldquoPanels paper and paper board form agriculturalresiduesrdquo Food and Agriculture Organization Rome Italy)e FAO Annual Pulp and Paper Capacity Survey 2007

[22] S M Arora ldquoHand book on pulp and paper industries rawmaterials required Indiardquo 1990

[23] F Lina ldquoConservation of Chines shadow puppets of Kwok oncollection- Funacaoorienterdquo in Proceedings of the ICOMConservation Committee Work Groups of Leather and RelatedMaterial and Legal Issues Athens Greece April 2004

[24] E Halasz-Csiba ldquoFrom woolen sheep leather to gilt leatherhangings a historical technical and lexical approach of Basanin Francerdquo in Proceedings of the ICOM Conservation Com-mittee Work Groups of Leather and RelatedMaterial and LegalIssues p 47 Athens Greece April 2004

[25] P S Storch ldquoCuratorial care and the handling of leathermaterials part 1 tanned objectsrdquo Conservation Notes vol 17pp 1ndash4 1987

[26] P E Guld Beak Leather its Understanding and Care Nashvillep 100 American Association for State and Local HistoryNashville TN USA 1969

[27] M Souckova ldquoInfluence of the environment humidity and ofwater used in conservation on treatment on external prop-erties of leather and parchmentrdquo Leather Conservation Newsvol 14 no 1 p 9 1998

[28] H J Plenderleith =e Preservation of Leather Bookbindingp 201 Great Britain the Trustees of the British MuseumLondon USA 1970

[29] C S Tumosa M F Mecklenburg W D Erhardt andM H McCormick-Goodhart ldquoA discussion of research onthe effects of temperature and relative humidity on museumobjectsrdquo WAAC Newsletter vol 18 no 3 pp 19-20 1996

[30] R R A Hassan ldquoA ldquoTafsir AL Khazenrdquo manuscript (17th

century AD) a technical studyrdquo International Journal ofConservation Science vol 6 no 3 pp 369ndash382 2015

[31] R R A Hassan M F Ali and A-G A Fahmy ldquoUse of SEMFTIR and amino acid analysis methods to assess the damageof some historical leather bindings from the xixth centurystored in national archive Cairordquo International Journal ofConservation Science vol 9 no 1 pp 127ndash136 2018

[32] ISO 6588-1 ldquoPaper board and pulpsmdashdetermination of pH ofaqueous extractsmdashPart 1 cold extractionrdquo 2012

[33] R Attalla and D Vanderhart ldquoNative cellulose composite oftwo distinct crystalline formsrdquo Science vol 223 no 4633pp 283ndash285 1984

[34] A S Ortiz-Miranda A Domenech-Carbo M T Domenech-Carbo L Osete-Cortina F Bolıvar-Galiano and I Martın-Sanchez ldquoAnalyzing chemical changes in verdigris pictorialspecimens upon bacteria and fungi biodeterioration usingvoltammetry of microparticlesrdquoHeritage Science vol 5 no 1pp 1ndash17 2017

[35] P Calvini and A Gorassini ldquoFTIR-deconvolution spectra ofpaper documentsrdquo Restaurator vol 23 pp 48ndash66 2002

[36] M F Abdel-Haleim A A Sakr M F Ali M F Ghaly andC Sohlenkamp ldquoCharacterization of Streptomyces isolates

Journal of Chemistry 9

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry

causing colour change of mural paintings in ancient EgyptiantombsrdquoMicrobiologial Research vol 168 no 7 pp 428ndash437 2013

[37] S Scheerer O OrtegandashMorales and C Gaylarde ldquoChapter 5microbial deterioration of stone monuments-an updatedoverviewrdquo Advances in Applied Microbiology vol 66 pp 97ndash139 2009

[38] A B Strzelczyk J Kuroczkin and W E Krumbein ldquoStudieson the microbial degradation of ancient leather bookbindingsPart Irdquo International Biodeterioration vol 23 no 1 pp 3ndash271987

[39] R R A Hassan ldquo)e restoration of two historic leatherbindings according to a new strategyrdquo Journal of the Instituteof Conservation vol 42 no 3 pp 210ndash225 2019

[40] A M B Olsson T Calligaro S Colinart et al ldquoMicro-PIXEanalysis of an ancient Egyptian papyrus identification ofpigments used for the ldquoBook of the Deadrdquordquo Nuclear Instru-ments and Methods in Physics Research Section B Beam In-teractions with Materials and Atoms vol 181 no 1-4pp 707ndash714 2001

[41] L Lee and S Quirke ldquoPainting materials ancient Egyptianmaterials and technologyrdquo Edited by P T Nicholson andI Shaw Eds pp 104ndash117 Cambridge University PressCambridge UK 2000

[42] B Wagner M L Donten M Donten E BulskaA Jackowska and W Sobucki ldquoAnalytical approach to theconservation of the ancient Egyptian manuscript ldquoBakai Bookof the Deadrdquo a case studyrdquoMicrochimica Acta vol 159 no 1-2 pp 101ndash108 2007

[43] S Nagashima M Kato T Kotani et al ldquoApplication of theexternal PIXE analysis to ancient Egyptian objectsrdquo NuclearInstruments and Methods in Physics Research Section B BeamInteractions with Materials and Atoms vol 109-110pp 658ndash661 1996

[44] M Aru L Burgio and M S Rumsey ldquoMineral impurities inazurite pigments artistic or natural selectionrdquo Journal ofRaman Spectroscopy vol 45 no 11-12 pp 1013ndash1018 2014

[45] M Zotti A Ferroni and P Calvini ldquoMycological and FTIRanalysis of biotic foxing on paper substratesrdquo InternationalBiodeterioration amp Biodegradation vol 65 no 4 pp 569ndash5782011

[46] H E Ahmed and S S Darwish ldquoEffect of museum conditionson historical dyed silk fabric with madder dyerdquo Journal ofPolymers and the Environment vol 20 no 2 pp 596ndash6062002

[47] M Schwanninger J C Rodrigues H Pereira andB Hinterstoisser ldquoEffects of short-time vibratory ball millingon the shape of FT-IR spectra of wood and celluloserdquo Vi-brational Spectroscopy vol 36 no 1 pp 23ndash40 2004

[48] R R A Hassan ldquoBehavior of archeological paper aftercleaning by organic solvents under heat accelerated ageingrdquoMediterranean Archaeology and Archaeometry MediterraneanArchaeology and Archaeometry vol 15 no 3 pp 141ndash1502015

[49] T Łojewski K Zieba A Knapik J Bagniuk A Lubanska andJ Łojewska ldquoEvaluating paper degradation progress Cross-linking between chromatographic spectroscopic and chem-ical resultsrdquo Applied Physics A vol 100 no 3 pp 809ndash8212010

[50] Y Liu S Kokot and T J Sambi ldquoVibrational spectroscopyinvestigation of Australian cotton cellulose fibrespart 2 aFourier transform near-infrared preliminary studyrdquo =eAnalyst vol 123 no 8 pp 1725ndash1728 1998

[51] R Michele S Dusan and M James Infrared Spectroscopy inConservation Science Scientific Tools for Conservation )eGetty Conservation Institute Los Angeles CA USA 1999

10 Journal of Chemistry