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Ethylene Oxide Residues in Fumigated Books - a First Result of the Project Men and Books : Ethylene Oxide Residues in Fumigated Books - a First Result.

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Presentation on theme: "Ethylene Oxide Residues in Fumigated Books - a First Result of the Project Men and Books : Ethylene Oxide Residues in Fumigated Books - a First Result."— Presentation transcript:

1 Ethylene Oxide Residues in Fumigated Books - a First Result of the Project Men and Books : Ethylene Oxide Residues in Fumigated Books - a First Result of the Project Men and Books : Patricia Engel & Katja Sterflinger EU grant /

2 In every archive/library in Europe we find - microorganisms - acidic paper - ink corrosion - vegetabil tanned leather Horn I conference 2011 confirmed the need for research in these subjects and defined even more urgent research subjects

3 Mould on paper, leather, siels, etc.

4 Reasons New infestation New infestation Environment not clean enough Environment not clean enough Environment too wet Environment too wet Environment too warm Environment too warm Microclimate Microclimate Old infestation Old infestation

5 Recommendation for the museum/library/archive Good, i.e. individual house keeping policy Good, i.e. individual house keeping policy Stop sorce: Renovation of building / wet areas etc. Stop sorce: Renovation of building / wet areas etc. Cleaning of books by conservators or staff advised by conservators (health and safety measures!) Cleaning of books by conservators or staff advised by conservators (health and safety measures!) Repacking Repacking Regular control in future - climate monitoring etc. Regular control in future - climate monitoring etc.

6 Active measures Dry cleaning (HEPA Filter) Dry cleaning (HEPA Filter) Alcohol Alcohol Gamma rays Gamma rays Energy Energy Ethylene oxide Ethylene oxide But ethylene oxide treatment of paper is not allowed anymore in the EU since 1st September But ethylene oxide treatment of paper is not allowed anymore in the EU since 1st September from 1st September 2013 on EO may only be used according to Article 56 of the BPR (research and development) from 1st September 2013 on EO may only be used according to Article 56 of the BPR (research and development) If the use of EO as book fumigant on a regular basis is intended, ethylene oxide has to be included in. Annex I of the BPD and authorised as biocidal product first. If the use of EO as book fumigant on a regular basis is intended, ethylene oxide has to be included in. Annex I of the BPD and authorised as biocidal product first.

7 I Questions in this project Does EO stay in the books, if so how long? Does EO stay in the books, if so how long? Does off fuming dose pose a risk in readers? Does off fuming dose pose a risk in readers? Did EO kill the mold? Did EO kill the mold? Did EO damage the material? Did EO damage the material?

8 Compilation of Publications on Ethyleneoxide in Paper Conservation Hanus, J., Mináriková, J., Ďurovič, M., Bacílková, B.: Influence of ethylene oxide fumigation on some properties of different types of paper. La Conservation: Une Science en evolution - Bilan et Perspectives. Actes des troisiémes journées internationales d'études de l'ARSAG, Paris, April 1997, p Richardin, P., Hanus, J., Bonnassies-Termes, S.: Rétention de l'oxyde d'ethylene dans les documents graphiques et photographiques désinfectés. Colloque Huilles essentielles et conservation des oeuvres d'art. Musée National des Arts et Traditions Populaires, Paris, 2-3 décembre Abstracts of presentations, p. 11. Hanus, J.: Determination of residual ethylene oxide and its desorption from different types of sterilized papers. Final Report. Centre de Recherches sur la Conservation des Documents Graphiques, Paris 1998, 100 p. Hanus, J., Richardin, P., Bonnassies-Termes, S.: Influence of ethylene oxide sterilisation on some photographic papers. ICOM Committee for Conservation, 12 th Triennial Meeting Lyon, 29 August - 3 September 1999, Preprints Volume II, p Hanus, J., Richardin, P., Bonnassies-Termes, S., Ďurovič, M., Kubelka, V.: Comparison of two different methods by head space gas chromatography for determination of residual ethylene oxide in sterilized papers. ICOM Committee for Conservation, 12 th Triennial Meeting Lyon, 29 August - 3 September 1999, Preprints Volume II, p Christina Meier; Karin Petersen: Schimmelpilze auf Papier. Ein Handbuch fur Restauratoren, biologische Grundlagen, Erkennung, Behandlung und Pravention, Tonning [a. o.]: Der Andere Verlag, 2006 Christina Meier; Karin Petersen: Schimmelpilze auf Papier. Ein Handbuch fur Restauratoren, biologische Grundlagen, Erkennung, Behandlung und Pravention, Tonning [a. o.]: Der Andere Verlag, 2006 The revenge of time: fungal deterioration of cultural heritage with particular reference to books, paper and parchmentemi. Environmental Microbiology (2011) Flavia Pinzari, Katja Sterflinger, The revenge of time: fungal deterioration of cultural heritage with particular reference to books, paper and parchmentemi. Environmental Microbiology (2011) Diplomarbeit Wien Abrahams, R.H. Recent studies with workers exposed to ethylene oxide, in: Jorkasky J.F., ed., Safe use Abrahams, R.H. 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Lancet 28: Rusch GM, Bast CB, Cavender FL (2009) Establishing a point of departure for risk assessment using Rusch GM, Bast CB, Cavender FL (2009) Establishing a point of departure for risk assessment using acute inhalation toxicology data. Regul. Toxicol. Pharmacol. 54: acute inhalation toxicology data. Regul. Toxicol. Pharmacol. 54: Schneider et al Reg. Tox. Pharm. 44/2, and Schneider et al Reg. Tox. Pharm. 44/2, and Snellings W, Weil C Maronpot R (1984): A two-year inhalation study of the carcinogenic potential of Snellings W, Weil C Maronpot R (1984): A two-year inhalation study of the carcinogenic potential of ethylene oxide in Fischer 344 rats, Tox. Appl. Pharm., 75, pp , 1984 ethylene oxide in Fischer 344 rats, Tox. Appl. Pharm., 75, pp , 1984 Snellings WM, Maronpot RR, Zelenak JP et al. (1982): Teratology study in Fischer 344 rats exposed to Snellings WM, Maronpot RR, Zelenak JP et al. (1982): Teratology study in Fischer 344 rats exposed to ethylene oxide by inhalation, Toxicol. Appl. Pharamacol., 64, ethylene oxide by inhalation, Toxicol. Appl. Pharamacol., 64, Snellings W, Zelenak J, Weil C (1982b): Effects on reproduction in Fischer rats exposed to ethylene Snellings W, Zelenak J, Weil C (1982b): Effects on reproduction in Fischer rats exposed to ethylene oxide by inhalation for one generation, Tox. Appl. Pharm., 63, pp oxide by inhalation for one generation, Tox. Appl. Pharm., 63, pp SCOEL – Scientific Committee on Occupational Exposure Limits (2012) Recommendation from the SCOEL – Scientific Committee on Occupational Exposure Limits (2012) Recommendation from the Scientific Committee onOccupational Exposure Limits.Risk assessment for ethylene oxide. Scientific Committee onOccupational Exposure Limits.Risk assessment for ethylene oxide. Scudamore KA, Heuser SG Ethylene oxide and its persistent reaction products in wheat flour Scudamore KA, Heuser SG Ethylene oxide and its persistent reaction products in wheat flour and other commodities: Residues from fumigation or sterilisation, and effects of processing. Pestic and other commodities: Residues from fumigation or sterilisation, and effects of processing. Pestic Sci 2: Sci 2: Sexton, R. J., E. V. Henson: J. industr. Hyg. 31, 297 (1949) Sexton, R. J., E. V. Henson: J. industr. Hyg. 31, 297 (1949) Sexton RJ, Henson EV Experimental ethylene oxide human skin injuries. Ind Hyg Occup Med Sexton RJ, Henson EV Experimental ethylene oxide human skin injuries. Ind Hyg Occup Med 32: : SHUPACK, J.L., ANDERSEN, S.R. and ROMANO, S.J. Human skin reactions to ethylene oxide. J. Lab. SHUPACK, J.L., ANDERSEN, S.R. and ROMANO, S.J. Human skin reactions to ethylene oxide. J. Lab. Clin. Med., 98, pp , 1981 Clin. Med., 98, pp , 1981 Tardif R, Goyal R, Brodeur J, Gerin M (1987) Species differences in the urinary disposition of some Tardif R, Goyal R, Brodeur J, Gerin M (1987) Species differences in the urinary disposition of some metabolites of ethylene oxide. Fundamental and Applied Toxicology, 9:448 –453. metabolites of ethylene oxide. Fundamental and Applied Toxicology, 9:448 –453. TANAKA, S., NAKAURA, S., KAWASHIMA, K., KASUYA, Y. and OMORI, Y. Studies on the hemolytic activity and TANAKA, S., NAKAURA, S., KAWASHIMA, K., KASUYA, Y. and OMORI, Y. Studies on the hemolytic activity and dermal irritability of ethylene oxide and its reaction products. Jap. J. Med. Instrum. 52(1), pp , 1982 dermal irritability of ethylene oxide and its reaction products. Jap. J. Med. Instrum. 52(1), pp , 1982 TGD (2003): Technical Guidance Document on Risk Assessment – European Communities 2003: TGD (2003): Technical Guidance Document on Risk Assessment – European Communities 2003: Thier R; Lewalter J, Kempkes M, Selinski S, Bruning T, Bolt H (1999): Haemoglobin adducts of Thier R; Lewalter J, Kempkes M, Selinski S, Bruning T, Bolt H (1999): Haemoglobin adducts of acrylonitrile and ethylene oxide in acrylonitrile workers, dependent on polymorphisms of the acrylonitrile and ethylene oxide in acrylonitrile workers, dependent on polymorphisms of the glutathione transferases GSTT1 and GSTM1. Arch Toxicol (1999) 73: 197―202 glutathione transferases GSTT1 and GSTM1. Arch Toxicol (1999) 73: 197―202 Thier, R., Balkenhol, T. Lewalter, J,. Selinski, Sl Dommermuth, A., Bolt, H.M. (2001) Influence of Thier, R., Balkenhol, T. Lewalter, J,. Selinski, Sl Dommermuth, A., Bolt, H.M. 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9 Report by Prof. Dr. habil. A. Strzelczyk Torun April – Aug April – Aug ,2 meter in total (261,2 m, 85 m in foulders, 13m notes) 346,2 meter in total (261,2 m, 85 m in foulders, 13m notes) The following measures were taken: The following measures were taken: 1. sources of damage were analysed, 1. sources of damage were analysed, The books were stored in wet/very humid conditions The books were stored in wet/very humid conditions The books were dusty, there are spores in the dust, a risk for human health The books were dusty, there are spores in the dust, a risk for human health 10 years ago (1984) the books were brought to dry rooms, but due to tight packing they dryed slowly 10 years ago (1984) the books were brought to dry rooms, but due to tight packing they dryed slowly Humidiy and temperature were measured in 50 books in Junly 1994, the rH was between 59 and 71 and the Temp. Between 19,5 and 23,4^C Humidiy and temperature were measured in 50 books in Junly 1994, the rH was between 59 and 71 and the Temp. Between 19,5 and 23,4^C The humidity of the air in the room was between % and the temperatureat 22,6 Centigrades The humidity of the air in the room was between % and the temperatureat 22,6 Centigrades 2. 9 books and 15 groups of archival documents were selected according to various criteria (sort of damage,,aterial composition, content) and model restoration was made, 2. 9 books and 15 groups of archival documents were selected according to various criteria (sort of damage,,aterial composition, content) and model restoration was made, 3. Microorganisms were analysed by microscopic observation directly on the books or in complicated cases on growth medium. The following species were found: Streptomyces, Geotrichum, Chaetomium, Acremoniella, Stachybotrys, Epicoccum, Stemphylium, Botrytis. Streptomyces and Geotrichum were found more often. 3. Microorganisms were analysed by microscopic observation directly on the books or in complicated cases on growth medium. The following species were found: Streptomyces, Geotrichum, Chaetomium, Acremoniella, Stachybotrys, Epicoccum, Stemphylium, Botrytis. Streptomyces and Geotrichum were found more often. 4. the entire collection plus the 9 books and 15 groups of archival material was packed and prepared for desinfection 4. the entire collection plus the 9 books and 15 groups of archival material was packed and prepared for desinfection Chamber for 20 m3, 10 kg Petrox, 5 days fumigation, then airwashing until EO detector did not show EO any more Chamber for 20 m3, 10 kg Petrox, 5 days fumigation, then airwashing until EO detector did not show EO any more The rooms were desinfected with 2% Aseptin M solution and treatment repeated after 10 days The rooms were desinfected with 2% Aseptin M solution and treatment repeated after 10 days 5. Fumigation with 90% EO and 10% CO2 (Petrox gas) 5. Fumigation with 90% EO and 10% CO2 (Petrox gas) 6. books were air washed and climatized, 6. books were air washed and climatized, In Swidnica In Swidnica 7. dust and microorganism spores were removed from the books in Sept (after the report was written) 7. dust and microorganism spores were removed from the books in Sept (after the report was written) 8. the effectivity of the desinfection was evaluated (report Nov. 1994) 8. the effectivity of the desinfection was evaluated (report Nov. 1994)

10 15 years later 2009 in Ossolineum alle alten Drucke (Signaturgruppe SD) und Handschriften (Signaturgruppe R) begast worden. „2010 durch Adam Wilga, der eine solche Begasungskammer erfunden hat, die übrigen Bücher begast (Signaturen 1,2,8000).“ „Wenn es um die Signaturen geht, nach denen Sie gefragt haben, handelt es sich um fortlaufende Signaturen (gemäß Katalog Dr. Górski).“ Waiting for data from Ossolineum Waiting for data from Ossolineum

11 MEN AND BOOKS For the selection of books several parameters were relevant: (1) moment of fumigation (17 fumigated in 2009, 11 fumigated in 2010) (2) material composition (11 printed books, 7 ms iron gall ink, 10 modern dye ink, 15 leather involved, 3 parchment involved, 11 textile involved, all book blocks paper of their time) (3) age of the book (2 18 th cent., 12 from 19 th cent. Rest 20 th cent.) (4) size of book (folio to octav) The books for ethylene oxide measurement were chosen aiming to get a representative average of all these features. This is especially important when it comes to transfer data into application Europe-wide and on an “average archive” at the end of the project. 28 volumes bound in leather, parchment, paper and textiles, dating from the 18 th, 19 th and 20 th century, thus representing also different sorts of paper as book block, ranging from folio to quart were selected by the Parish in Swidnica and brought to the European Research Centre for Book and Paper Conservation-Restoration in Horn. There these books were put into a chamber of inert synthetic material of 1 qm volume and stored under closed conditions for 60 days at 20 °C and 50%rel. H. MEN AND BOOKS For the selection of books several parameters were relevant: (1) moment of fumigation (17 fumigated in 2009, 11 fumigated in 2010) (2) material composition (11 printed books, 7 ms iron gall ink, 10 modern dye ink, 15 leather involved, 3 parchment involved, 11 textile involved, all book blocks paper of their time) (3) age of the book (2 18 th cent., 12 from 19 th cent. Rest 20 th cent.) (4) size of book (folio to octav) The books for ethylene oxide measurement were chosen aiming to get a representative average of all these features. This is especially important when it comes to transfer data into application Europe-wide and on an “average archive” at the end of the project. 28 volumes bound in leather, parchment, paper and textiles, dating from the 18 th, 19 th and 20 th century, thus representing also different sorts of paper as book block, ranging from folio to quart were selected by the Parish in Swidnica and brought to the European Research Centre for Book and Paper Conservation-Restoration in Horn. There these books were put into a chamber of inert synthetic material of 1 qm volume and stored under closed conditions for 60 days at 20 °C and 50%rel. H.

12 Books brought to Horn off gasing measured

13 Two different analysis methods were chosen to detect the off gassing ethylene oxide, a digital handheld device, Dräger X-am 5000, which turned out to be too rough (measuring range ppm, resolution 0.5 ppm, smallest possible detection 1 ppm; expected concentration below) and a GC/FID. For the later the measurement was passive with ORSA-tubes filled with activated carbon. The measurement lasted for 336 hours. Then the tubes were taken out, closed and sent to gas chromatography. The analysis was made with GC/FID with retention time catalogues and quantification via external calibration function. This standard working instruction is a modified NIOSH Working conditions: Gaschromatograph “Doppelsäulengerät Sichromat 1-4”; Injektion: split/splitless; 2.5µL splitted auf 2 wide-bore colums, 250°C, Colums: 30 m OPTIMA-WAX; 0.53 mm * 1.0 µm and 30 m OPTIMA 1; 0.53 mm *1.0 µm, Both detectors FID (250°C), Carrier gas Nitrogen: 2.5 mL/min, burning gas synth. air: 300 mL/min, Hydrogen: 25 mL/min, stove temperature 45°C isotherm 10 min, 45°C to 180°C in 5°C/min; 180°C isotherm 13 min, 180°C to 200°C in 10°C/min, 200°C isotherm 13 min. The method is based on the international method NIOSH 1612 (http://www.cdc.gov/n iosh/docs/ /pdfs/1612.pdf) iosh/docs/ /pdfs/1612.pdfhttp://www.cdc.gov/n iosh/docs/ /pdfs/1612.pdf

14 Umweltbundesamt Takes the influence via inhalation for the gratest risk Takes the influence via inhalation for the gratest risk Not so much touching Not so much touching Not so much oral Not so much oral About Material I suggest to add several book blocks to the fumigation of dummies, as to have more substance to catch the EO gas possibly and get more realistic and controlled measurement for our conclusions.

15 Workflow Dummies Dummy A 1Dummy A 2Dummy A 3Dummy A 4Dummy A 5Dummy A 6Dummy A7Dummy 8 Nach der Herstellung direkt für Ethylenoxidbe gasung ohne Zwischenschri tte Nach der Herstellung direkt für Mikroorganismen beimpfung ohne Zwischenschritte Nach der Herstellung direkt für Mikroorganismen beimpfung ohne Zwischenschritte ReferenzNach der Herstellung direkt für Alterung Nach der Herstellung direkt für Alterung Dummy A 5Dummy A 6Dummy A 7Dummy A8 Alterung Referenz Alterung Weiter zur Ethylenoxid begasung Alterung Weiter zur Mikro Organismen beimpfung Alterung Weiter zur Mikro Organismen beimpfung Dummy A2Dummy A3 Dummy A 7Dummy A 8 Direkt vom ERC kommend zum Beimpfen Direkt vom ERC kommend zum Beimpfen Beiter zum Ethylenoxid begasen Von der TU Graz kommend zum Beimpfen Referenz Von der TU Graz kommend zum Beimpfen Weiter zum Ethylen oxid Dummy A 1 Dummy A 3 Dummy A 6 Dummy 8 Kommt direkt aus dem ERC ohne Vorbehandlun g Ist nicht gealtert, sondern Nur beimpft Kommt direkt aus der TU Graz Ist nur gealtert Kommt von der BOKU ist gealtert Und beimpft

16 Suggestion book block for more volume !

17 Aims ERC took over in the project: - measuring off-gassing ethylene oxide - measuring off-gassing ethylene oxide - evaluation of toxicity(Umweltbundesamt) - evaluation of toxicity(Umweltbundesamt) - provide dummies - provide dummies - analysis of the parchment&leather - analysis of the parchment&leather - interpretation of analyse-data - interpretation of analyse-data - development of guidelines for the restoration - development of guidelines for the restoration - develop recommendations for the handling of mouldy heritage&handling of ethylene oxide-fumigated heritage on paper, parchment and leather - develop recommendations for the handling of mouldy heritage&handling of ethylene oxide-fumigated heritage on paper, parchment and leather - suggestions of alternative methods to disinfect mouldy written/printed heritage - suggestions of alternative methods to disinfect mouldy written/printed heritage - disseminate the project results (website, journals, etc.) - disseminate the project results (website, journals, etc.) - organise the joint exhibition in coop. with the other partners - organise the joint exhibition in coop. with the other partners - organise the final conference in coop. with P5 - organise the final conference in coop. with P5. - organise the publication material in coop. with the partners (translation, distribution, etc.) - organise the publication material in coop. with the partners (translation, distribution, etc.) - distribution of results: professional journals, special meetings, conference, webpage, movable exhibition for specialists - distribution of results: professional journals, special meetings, conference, webpage, movable exhibition for specialists & laymen, local newspapers, TV, radio, underlining the benefit of EU funding; ERASMUS-students & laymen, local newspapers, TV, radio, underlining the benefit of EU funding; ERASMUS-students - workshops beyond project runtime - workshops beyond project runtime

18 Next steps -Work flow Graz BOKU Ossolineum -Shrinkage Temperature Measurement -Graz: Paper tests -Umweltbundesamt Results -BOKU results on fungi -Question: is the paper more disposed to new attack by the ethylene Oxide treatment or not?

19 HW Step 6 together with ICARUS: Step 6 together with ICARUS: Digitization(50000 files) of the material for research work in the project & making it accessible for all on the internet Start on 11th March 2013

20 Acknowlegement For the information about the books: Bozena Pytel, Reverend Waldemar Pytel, Sonja Stankowski, Dr. Stephan Aderhold Umweltbundesamt: Dr. Elisabeth Fassold, DI Isabel Peißl, Dr. Maximilian Kinzl, Dr. Martin Paparella Dräger Safety AG & Co. KGaA: Thomas Krebs and Dr. Dirk Rahn-Marx ERC: Shirin Jacoby, Bogna Gorniak, Marta Cieplinska, Cristina Cicero


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