Volatile Organic Compounds in libraries atmosphere: effects on the written and printed cultural heritage.

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1 Volatile Organic Compouns in libraries atmosphere: effects on the written an printe cultural heritage. Thi-Phuong NGUYEN National Library of France

2 Libraries an archives : pollution inoors Concentration (ug/m3) Magazines in boxes 19th newspapers in boxes 19th an 20th books Formalehye 17,7 18,6 17,3 benzalehye 41, ,1 hexanal 13,2 8,7 2,7 Alcanes 1,4 1,7 1,0 Acetic aci Formic aci <10 <10 <10 Sulfuric aci, hyrogen sulfie <10 <10 <10 Pollutants emitte by : The collections themselves (acetic aci) Some kins of conservation boxes

3 Micro an macro environments? Effect of the pollution on the lifetime of paper-base collections? Quality control of the conservation materials

4 Quality control of materials ISO : Boxes, file covers an other enclosures, mae from cellulosic materials, for storage of paper an parchment ocuments «Materials use shall not contain or form any substances [ ] which may be harmful to the ocuments being store.»???

5 Aim of the stuy Analysis of the composition of boars an papers (ph, fibers, lignin content, alcali reserve) Total sulfur quantification (UV fluorescence) SEM-EDS examination (filling an loaing materials) Analysis of the VOC s they emit (SPME-GC-MS) Stuy of impact of these VOC s on paper cellulose (SEC)

6 Composition : results All the boars stuie have alcaline ph an alcali reserve Lots of them are mae from recycle materials. Among them, only 2 o not have lignin Only the certifie «conservation grae» boars just contain calcium carbonate as inorganic species. Silicates, potassium, magnesium, soium, sulfur containing inorganic species are observe in the others boars an especially, in those mae from recycle materials.

7 Sulfur analysis Total Sulfur content : UV fluorescence of SO2 after complete burning of the sample at 1000 C in O2-Ar (0,0001-0,3%) Sulfur istribution : SEM-EDX mapping

8 Sulfur content Total sulfur content 0,03 % to 0,18 % Higher contents : boars mae from recycle material

9 SEM-EDX EDX elemental mapping : sulfur istribution Sulfur Calcium Sulfur Calcium sulfate (CaSO4) gypsum

10 CORRELATION BETWEEN SULFUR CONTENT, VOLATILES AND EFFECTS ON PAPER CELLULOSE?

cellulose Dp * ASTM D6819-02 :2007Stanar Test Metho for Accelerate

11 Artificial ageing 100 C -50 % relative humiity 5 ays* Size exclusion chromatography of age Whatman paper cellulose Determination of cellulose Dp * ASTM D :2007Stanar Test Metho for Accelerate Temperature Aging of Printing an Writing Paper by Dry Oven Exposure Apparatus

12 Sulfur content an Dp of cellulose after artificial ageing More egrae Decrease of paper cellulose Dp Dp par rapport (Dp/Dp au unage Dp u Whatman témoin Whatman paper) non vieilli 1,2 1 0,8 0,6 0,4 0,2 0 Papier test Boar A vieilli + carton (recycle) Fibre 2000 Papier test Boar B vieilli + carton (recycle) Brun Onulé 2 Papier test Boar C vieilli + carton (recycle) Fibre 2008 Papier test Boar D vieilli + carton (recycle) Brun Onulé 1 Papier test Boar E vieilli + carton (recycle) Gris Recyclé Papier test Papier test Papier test Papier test non Boar F Reference Boar G Reference vieilli + carton vieilli + Papier vieilli + carton vieilli (conservation) (age) (conservation) (unage) Brun Whatman Aroise Conservation Conservation

13 Sulfur content an Dp of cellulose after artificial ageing Decrease of paper cellulose Dp Dp par rapport (Dp/Dp au unage Dp u Whatman témoin Whatman paper) non vieilli 1,2 1 0,8 0,6 0,4 0,2 0 0,18 % Papier test Boar A vieilli + carton (recycle) Fibre ,18 % Papier test Boar B vieilli + carton (recycle) Brun Onulé 2 0,18 % 0,17 % 0,08 % Papier test Papier test Papier test Boar C Boar D Boar E vieilli + carton vieilli + carton vieilli + carton (recycle) (recycle) (recycle) Fibre 2008 Brun Onulé 1 Gris Recyclé 0,03 % 0,03 % Papier test Papier test Papier test Papier test non Boar F Reference Boar G Reference vieilli + carton vieilli + Papier vieilli + carton vieilli (conservation) (age) (conservation) (unage) Brun Whatman Aroise Conservation Conservation

14 VOC s analysis Extraction 1h 60 C hea space SPME fiber (85um Carboxen/PDMS stable flex) GC-MS analysis Boar B Boar G Boar C Boar A Peak area (uv) Acetic aci butanol-1 Pentanal Hexanal Furfural Heptanal Benzalehye Octanal Acetophenone Nonanal Decanal

15 The role of VOC s

16 The role of VOC s

17 Conclusions It is very ifficult to anticipate any simple relationship between VOC s emissions, composition of a material, an its effects on paper-base artefacts «Performance tests» more interesting approach

Photoactivity test* (PAT) Colloïal silver films Photographic

Comparison with a control incubate with Whatman filter paper.

boar * ISO Stanar 18902: Imaging Materials Processe

18 Photoactivity test* (PAT) Colloïal silver films Photographic paper 86% HR-70 C 2 weeks Photographic ensity measurements. Comparison with a control incubate with Whatman filter paper. High % image interaction ifference = Chemical effect of the boar * ISO Stanar 18902: Imaging Materials Processe photographic films, plates, an papers Filing enclosures an storage container

19 Photoactivity test vs Molecular weight of cellulose interraction with colloïal silver [x10] (%) Mw x10-3 (g/mol) Boar A Boar 1 Boar 2 Boar B Boar 3 Boar 4 Boar D Boar 5 Boar 6 Boar 7 Boar E Boar G Boar 9 Boar 10 Whatman Boar 11 Boar 12 reference For most of the boars teste, goo correlation between the PAT results an the harmfulness on paper cellulose

20 Conclusion Next future : evelopment of a photo-cellulo-activity test?

21 Acknowlegement Michel Dubus (C2RMF) Véronique Rouchon (CRCC) Maroussia Duranton (BnF) Delphine Bequignon (BnF) Valentin Rottier (BnF)

(September ) Instructors: Bertrand Lavédrine, Director, CRCC Léon-Bavi Vilmont, Chemist, Head Audio/Visual Department

(September ) Instructors: Bertrand Lavédrine, Director, CRCC Léon-Bavi Vilmont, Chemist, Head Audio/Visual Department SEMINAR AT THE CENTRE DE RECHERCHE SUR LA CONSERVATION DES COLLECTIONS (CCRC) FOR THE HERMITAGE STAFF (September 20-2010) Instructors: Bertrand Lavédrine, Director, CRCC Léon-Bavi Vilmont, Chemist, Head