SPECTROPHOTOMETRIC MEASURMENTS TO DETECT THE ROLE OF POLYMERS AND RESINS IN PREVENTION OF FUNGAL DETERIORATION OF ANCIENT EGYPTIAN LINEN TEXTILES

Omar Abdel-Kareem, Jadwiga Szostak-Kotowa Cracow University of Economics Department of Microbiology Sienkiewicza 5 30-033 Krakw Poland Abstract In this study Egyptian linen textile samples treated by 12 different polymers and resins that are important in preserving ancient Egyptian linen textiles were studied. The treated samples were deteriorated by 7 selected active fungal strains isolated from archaeological Egyptian linen textile samples. The fungal deterioration produced was assessed visually. Also, spectrophotometric measurements were used to follow the change in brightness and colour differences of the deteriorated samples. The results obtained showed that most of the tested polymers reduce the fungal growth of linen textiles but do not prevent the deterioration at all. Paraloid B72, Beva 371 and starch carbamate are the most tested polymers resistant to fungal attack. Acryloid F-10 and Mowilith are the least tested polymers resistant to fungal attack. Most of tested polymers improve the rot resistance of linen textiles against most of the tested fungi. Trichoderma viride and Penicillium funiculosum are the most active fungi in the deterioration of most of the tested polymers. Aspergillus terrus, Penicillium asperum, Alternaria tenuissima, Chaetomium globosum and Aspergillus nidulans are the least active fungi in the deterioration of most of the tested polymers. Keywords Linen, textiles, polymers, prevention, deterioration, fungi, spectrophotometric measurements Introduction Highly degraded textile artefacts present a problem for the textile conservators because there is no entirely satisfactory treatment for them. Often conventional stitching techniques cannot be used because the needle and sewing threads may break the fragile textile yarns (Halvorson and Kerr, 1994). So polymers and resins have been widely used in textile conservation (Beecher, 1979: Blum, 1982: Masschelein-Kleiner, and Bergiers, 1984, and Verdu, et al 1984: Koestler and Santoro, 1988: Keyserlingk, 1990: AbdelKareem, 1995: Landi, 1998:). It has generally been acknowledged that synthetic resins for use in textile conservation should meet special requirements (Abdel-Kareem preprint). The choice of these resins must be made after carefully evaluating their physical and chemical characteristics, as there is a definite correlation between these characteristics and the possibility of attack by biological agents. The potential for a polymer to play as a food source for microbes must be understood before an intelligent choice of an

appropriate consolidation can be made for a given application. Selection of polymers and resins based only on non-biological criteria may initially succeed in minimising the physical and chemical deterioration of the substrate, but in the longer term may lead to enhanced biological degradation and a worse deterioration condition than that before treatment (Santoro and Koestler, 1991). Resins of both natural and synthetic origin may be destroyed by biological agents, and therefore can also stimulate the growth of microorganisms on textiles. Synthetic resins are more resistant or even impervious to microbial degradation (Kowalik, 1980). Additives used in order to give resins certain characteristics (such as plasticizers) can in fact be a source of nutrition for some biological agents (Gillatt, 1990). The prevention of the deterioration of polymers and resins used in the conservation and restoration of textiles is one of widespread interest. While many studies have considered the physical and chemical mechanisms that contribute to this deterioration, fewer have focused on the particular problem of biological attack on these materials (Santoro and Koestler, 1991). However most of the problems in using polymers in the field of textile conservation are that these materials cause stiffness to textiles. Thus, it is recommended that these textiles must be displayed or conserved in high relative humidity (Abdel-Kareem, 1995). For this reason one can think that these textiles will be liable to fungal deterioration. Also, it is common that most of polymers used in the conservation of textiles are considered copolymers, and they often have additives such as plasticizers. It is known that these additives may promote fungal growth on textiles. This study aims to evaluate the use of polymers and resins used in the consolidation of ancient Egyptian linen textiles from the microbiological point of view and from a conservators perspective. This study is considered as an initial test for assessing the susceptibility of linen textiles treated with polymers and resins to fungal deterioration and to detect the role of polymers and resins in the prevention of the biodeterioration of ancient Egyptian linen textiles. Materials and Methods. Fabrics Unbleached Egyptian linen fabric supplied by Egellan Company (Alexandria - Egypt) is used in this work and its specifications are shown (table 1). Table 1. Specifications of used linen
Structure Colour Nominal Wt. Thread/cm. Liner density (Tex.) warp 20 weft 20 % of elongation Tensile strength 29.08 N/mm2

Plain weave 1/1

Grey

g/m 260

warp 20

weft 16

30.57

Fungal Strains In this study 7 active fungal strains submitted by Abdel-Kareem, et al 1997, were used. These strains are (1) Aspergillus nidulans, (2) Aspergillus terrus, (3) Penicillium asperum, (4) Alternaria tenuissima, (5) Chaetomium globosum, (6) Trichoderma viride

and (7) Penicillium funiculosum, Used Polymers and Resins The materials selected were polymers and resins currently used in conservation or materials that could be used in the future (Beecher, 1979: Blum, 1982: MasscheleinKleiner and Bergiers, 1984: Verdu, et al 1984: Sayed, et al 1988: Keyserlingk, 1990: Abdel-Kareem, 1995: Down, et al 1996: Land,i 1998: Abdel-Kareem preprint). Most of the materials utilised for study are selected examples of polyvinyl acetate, polyacrylic resins (table 2). Table 2. Used Polymers and Resins
Chemical Name 1 2 3 4 5 6 7 8 9 10 11 12 Vinyl acetate/acrylic ester copolymer Vinyl acetate/dibutyle maleate copolymer Ethyl acrylate/ methyl methylacrylate Butyl acrylate/ methyl methylacrylate Ethyl acrylate/ methyl methylacrylate Butyl methylacrylate Butyl methylacrylate Soluble Nylon Keton resin N Methyl hydroxy ethyl cellulose Hydroxypropylcellulose Starch carbamate Trade Name Mowilith DM5 (E) Mowilith DMC2 (E) Paraloid B72 (SD) Lascaux 360 HV (E) Plextol B-500 (E) Acryloid F-10 (SN) Plexisol P-550 (SN) Calaton CA (SD) Beva 371 (SN) Tylose MH300 (SD) Klucel G (SD) (SD) Producer Hoechst Hoechst Rohm and Haas] Lascaux Restauro Lascaux Restauro Rohm and Haas Lascaux Restauro Imperial Chemical Industrials ICI Lascaux Restauro Hoechst Lascaux Restauro prepared according to (Sayed, et al 1988) Conc. % 10 10 6 10 10 10 10 6 10 4 4 6

(E) = Emulsion; (SD) = Solid; (SN) = Solution

Polymer and Resins Preparing The polymers and resins were used in usual proportions for textile conservation (Beecher, 1979: Masschelein-Kleiner and Bergiers, 1984: Verdu, et al 1984: Sayed, et al 1988: Keyserlingk, 1990: Abdel-Kareem, 1995: Landi, 1998: Abdel-Kareem preprint). (Mowilith DM5 1part + Mowilith DMC2 1part) 10% vol.: vol. in distilled water. Paraloid B72 6% in Acetone. Lascaux 360 HV (E) 10% vol.: vol. in distilled water. Plextol B-500 (E) 10 % vol.: vol. in distilled water. Acryloid F-10 (SN) 10% vol.: vol. in Acetone. Plexisol P-550 (SN) 10% vol.: vol. in Acetone. Calaton CA (SD) 2% in Ethyl alcohol (70%). Beva 371 (SN) 10% vol.: vol. in Acetone. Tylose MH300 (SD) 4% in distilled water. Klucel G was prepared according to (Abdel-kareem 1995) 4% in distilled water. Starch carbamate prepared according to Syad, et al 1988, 6 % in distilled water. Test Procedure

The fabric was first washed in sterilised distilled water and was dried at ambient temperature. The samples were soaked in these preparations and were dried at ambient temperature.

Treatment of Linen with Fungi The tests are performed in 90mm diameter Petri dishes on solid medium (Czapek-Dox agar modified) of the following composition (table 3). The medium was inoculated with spore suspension (14-day old culture) of test fungus. The spore suspension of each fungus was spread on the surface of the medium. For each test samples of linen textiles (5x5cm) were put into the infected medium. The plates were incubated at 28C. Two weeks later, the samples of textile were picked out and washed with water to remove mycelium then they dried at ambient room temperature. Specimens were conditioned at 21 2 C and 65 % 2 RH for 2days before testing. Table 3. Chemical Composition of media used Name of Media Chemical Composition Medium of Czapek-Dox NaNO3 agar modified KH2PO4 MgSO4.7H2O KCl FeSO4 Agar Distilled water Method of Observation. Visual Assessment 0The extent of fungal growth was assessed visually and recorded in accordance with the scheme specified in the standard (i.e. no growth: O; heavy growth: 5). And so, a visual, subjective assessment of the colour change of the bleached and unbleached linen textile samples that had been affected by fungi in the laboratory was obtained after 2 weeks. Reflection Spectra Reflection spectra was recorded for the treated and the control linen samples in the visible range (360-800nm) by a Shimadzu Double Beam UV-2101PC Spectrophotometer Equipped with ISR48 Intergating Sphere, using barium sulphate as a reference (a white standard). The reflectance of both front side and back side of each specimen was measured. Brightness and Colour Difference Evaluation In order to determine the relative rate of colour change of the bio-deteriorated samples, the reflectance values were inserted into a computer program which then calculated the CIELAB colour co-ordinates for L* co-ordinate refers to the lightness or darkness. In reference to this co-ordinate, black would read as zero, and white would read as 100. Both a* and b* co-ordinates were calculated too. To evaluate the effect of each fungi on

Weight or Volume 2g. 7g. 0.3g. 0.5g. 0.5g. 20g. 1000 ml.

pH 6.3

treated linen fabrics, it was as necessary to calculate the colour change () from the specific L, a, and b values. Calculation of total colour change (E) was achieved by the use of the following equations: E = [(L)2 + (a)2 + (b)2]0.5 Results and Discussion. Visual Assessment The results of visual assessment of fungal growth on untreated and treated samples in table (4) show that all tested polymers had reduced the fungal growth. The degree of fungal growth depends on both the type of the polymer and the fungal species. For example samples treated with Paraloid B72, Plexisol P-550, Calaton CA, Beva 371, Tylose MH300, Klucel G, and starch carbamate showed a noticeable reduction in the growth of Aspergillus nidulans. Samples treated with Mowilith, Lascaux 360 HV, Plextol B-500, and Acryloid F-10 did not show any noticeable reduction of the growth of the same fungus. Whereas samples treated with Klucel G, showed the greatest degree of reduction in growth of Aspergillus nidulans, Aspergillus terrus, Penicillium asperum, Trichoderma viride and Penicillium funiculosum, while the least degree of reduction in growth of Alternaria tenuissima, and Chaetomium globosum. Table 4. Degree of fungal growth on consolidated linen samples that had been deteriorated by tested fungi Polymer Fungi 1 Without treatment Mowilith Paraloid B72 Lascaux 360 HV Plextol B-500 Acryloid F-10 Plexisol P-550 Calaton CA Beva 371 Tylose MH300 Klucel G ++++ +++ ++ +++ +++ +++ + +++ ++ ++ + 2 +++ +++ ++ +++ +++ +++ +++ ++ ++ +++ ++ 3 +++ ++ + ++ ++ ++ + ++ + + ++ 4 ++++ +++ ++ +++ +++ +++ +++ +++ ++ ++ +++ 5 ++++ +++ ++ +++ ++ +++ +++ +++ +++ +++ +++ 6 +++ ++ + ++ ++ ++ + ++ + + ++ 7 +++ ++ ++ ++ ++ ++ + + + ++ ++

Starch + ++ ++ ++ ++ + + carbamate *Symbols indicate the degree of fungal growth on consolidated linen samples (50mm2); (+) indicates slight growth (less than 30% of the area of the test sample); (++) good growth (greater than 30% but less than 60% of the area of the test sample); (+++) very

good growth (greater than 60% but less than 80% of the area of the test sample); (+++ +) excellent growth (greater than 80% of the area of the test sample). Reflection Spectra The results of reflection spectra of all samples show that most of samples deteriorated by tested fungi became darker than the samples treated with different polymers except samples deteriorated by Trichoderma viride and Penicillium funiculosum. The results in figs (1,2) show the most and the least changes in the reflection spectra of treated and untreated samples, which were previously deteriorated by tested fungi. These results show that most of tested polymers had reduced the changes in the reflection spectra of samples deteriorated by Aspergillus terrus, Penicillium asperum, Alternaria tenuissima, Chaetomium globosum and Aspergillus nidulans, especially Paraloid B72, Beva 371 and starch carbamate. Brightness (L) Table (5) shows the values of the brightness (L) of treated and untreated samples before and after deterioration by fungi. These results show that most of samples deteriorated by tested fungi became darker than the samples treated with different polymers except samples deteriorated by Trichoderma viride and Penicillium funiculosum. From these data it is clear that samples treated with Paraloid B72, Beva 371, Calaton CA, Plexisol P-550 and starch carbamate showed the least changes in brightness (L). While samples treated with Mowilith, Acryloid F-10 showed the most changes in brightness (L). Also, the results show that Trichoderma viride and Penicillium funiculosum are the most active fungi on most of the tested polymers.
Table 5. The brightness (L) of linen treated by polymers and damaged by several fungi
Polymer side Without treatment Back Front Mowilith Back Front Paraloid B72 Back Front Lascaux 360 HV Back Front Plextol B-500 Back Front Acryloid F-10 Back Front 50.24 50.24 43.20 43.20 43.52 43.52 42.93 42.93 42.26 42.26 42.17 42.17 1 21,51 29,60 40.15 46.46 36.50 50.52 42.87 32.41 48.70 38.31 51.85 41.78 2 29,14 24,04 47.25 42.96 40.80 41.70 35.91 36.43 35.88 40.54 41.53 52.50 3 20,23 21,14 37.11 46.91 42.79 51.74 50.55 45.05 48.69 43.54 46.43 52.42 Fungi 4 33.20 23.66 31.75 28.98 47.98 50.61 47.14 38.90 46.46 45.03 37.16 40.03 5 35,82 35,82 31.56 46.91 47.07 50.64 38.85 45.21 45.70 51.93 33.53 43.97 6 40,06 40,59 44.77 46.20 33.92 40.72 38.22 32.75 39.82 56.36 48.50 49.30 7 25,69 30,07 36.45 46.38 41.44 51.44 51.00 38.11 49.19 53.80 35.11 46.62

Plexisol P-550

Back Front

44.60 44.60 53.18 53.18 51.04 51.04 47.53 47.53 47.78 47.78 48.25 48.25

53.65 44.58 42.34 52.10 32.41 50.58 48.21 48.19 48.91 44.02 50.12 49.88

54.44 43.54 46.45 54.48 43.35 34.29 42.12 36.25 48.02 42.69 43.80 41.33

43.48 43.81 37.05 48.12 46.00 55.75 44.09 50.12 53.81 48.12 48.29 46.66

44.72 48.69 41.12 56.50 37.34 49.22 39.10 49.76 42.58 45.26 53.66 50.57

39.73 48.51 38.09 36.32 39.73 46.50 47.33 42.45 36.95 48.60 44.84 39.93

29.75 45.03 28.18 60.13 28.60 38.60 48.18 43.43 38.85 46.49 34.13 35.54

54.22 45.92 44.02 56.92 37.99 48.69 44.96 48.88 40.99 47.39 43.27 48.61

Calaton CA

Back Front

Beva 371

Back Front

Tylose MH300

Back Front

Klucel G

Back Front

Starch carbamate

Back Front

Colour change (E) Table (6) shows the values of the colour change (E) of treated and untreated samples deteriorated by fungi. It is obvious from the data that most of tested polymers reduce the colour change (E) of samples, especially Paraloid B72, Beva 371 and starch carbamate. Also, the results show that Trichoderma viride and Penicillium funiculosum are the most active fungi on most of tested polymers.
Table 6. The colour change (E) of linen treated by polymers and damaged by several fungi
Polymer side Without treatment Back Front Mowilith Back Front Paraloid B72 Back Front Lascaux 360 HV Back Front Plextol B-500 Back Front Acryloid F-10 Back 3.85 3.85 6.88 6.88 7.17 7.17 0.93 0.93 5.92 1 21,56 15,34 7.36 12.30 5.69 18.92 3.97 2.94 0.37 7.63 17.96 2 21,01 25,63 1.12 4.41 2.60 1.48 7.94 10.88 9.98 2.13 9.68 3 29,32 28,27 8.05 1.19 1.98 12.76 1.27 5.04 1.02 1.22 0.02 Fungi 4 27.97 36.17 30.89 33.26 2.73 1.31 3.09 6.55 0.83 4.04 11.40 5 30,42 41,58 6.72 1.12 11.19 11.34 9.42 3.63 8.72 2.91 25.56 6 7,53 8,25 0.65 3.80 17.76 21.29 20.22 30.83 8.62 0.24 6.19 7 19,38 13,68 7.09 0.59 5.44 2.18 6.35 1.54 18.09 -8.02 3.33

Front Plexisol P-550 Back Front Calaton CA Back Front Beva 371 Back Front Tylose MH300 Back Front Klucel G Back Front Starch carbamate Back Front

5.92 4.53 4.53 0.39 0.39 0.17 0.17 4.08 4.08 2.97 2.97 5.41 5.41

14.64 2.30 5.31 5.38 16.36 10.50 1.69 3.28 3.31 1.50 5.64 1.14 8.44

1.32 7.00 0.73 5.25 6.13 3.14 9.31 0.05 5.55 3.41 5.03 6.64 1.38

3.04 4.16 3.49 1.21 9.47 9.54 4.07 1.81 1.98 7.94 9,47 7.89 3.31

15.16 5.96 2.33 12.40 10.01 6.94 0.30 5.13 1.23 2.65 5.13 3.11 1.32

13.21 3.60 8.03 3.87 9.14 3.00 4.52 17.57 3.60 0.03 5.04 6.02 0.90

0.90 21.40 12.25 11.86 10.89 27.94 15.68 3.26 12.30 5.42 1.19 21.94 24.34

1.74 5.21 1.64 0.95 5.30 7.03 0.64 4.32 9.76 4.87 2.13 5.45 3.42

By comparing all the obtained results it is clear that most of the tested polymers reduce the fungal growth of linen textiles but do not prevent deterioration at all. Also the results show that Paraloid B72, Beva 371 and starch carbamate are the polymers, most resistant to fungal attack, and Acryloid F-10 and Mowilith are the polymers least resistant to fungal attack. These results are in agreement with the previous studies on bio-deterioration of resins used in the conservation field. These studies showed that starches, hydroxyethylcelluloce, and Acryloid F-10, are the least resistant to biological attack (Kowalik, 1980: Masschelein-Kleiner and Bergiers, 1984: Thomsen, 1984: Koestler and Santro, 1988: Santro and Koestler, 1991: Abdel-Kareem, 1995). While the most resistant to biological attack are polyvinyl alcohol, soluble nylon, starch carbamate, and starch aminate (Kowalik, 1980: Sayed et al, 1988). Conclusion Most of tested polymers reduce the fungal growth of linen textiles but do not prevent deterioration at all. Paraloid B72, Beva 371 and starch carbamate are the most resistant polymers to fungal attack Acryloid F-10 and Mowilith are the least resistant polymers to fungal attack among tested polymers Most of the tested polymers improve the resistance of linen textiles against most of the tested fungi. Trichoderma viride and Penicillium funiculosum are the most active fungi in the deterioration of most of the tested polymers. Aspergillus terrus, Penicillium asperum, Alternaria tenuissima, Chaetomium globosum and Aspergillus nidulans are the least active fungi in the deterioration of most of tested polymers.

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