Ethylene Oxide Residues in
Fumigated Books - a First Result of
the Project Men
and Books
:
EU grant 2012-0920/001-001
Patricia Engel & Katja Sterflinger
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
Mould on paper,
leather, siels, etc.
Reasons
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New infestation
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Environment not clean enough
Environment too wet
Environment too warm
Microclimate
Old infestation
Recommendation for the
museum/library/archive
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Good, i.e. individual house
keeping policy
Stop sorce: Renovation of
building / wet areas etc.
Cleaning of books by
conservators or staff advised by
conservators (health and safety
measures!)
Repacking
Regular control in future climate monitoring etc.
Active measures
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Dry cleaning (HEPA Filter)
Alcohol
Gamma rays
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Energy
Ethylene oxide
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But ethylene oxide treatment of paper is not allowed anymore in the EU since 1st
September 2006.
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.
I
Questions in this project
Does EO stay in the books, if so how
long?
 Does off fuming dose pose a risk in
readers?
 Did EO kill the mold?
 Did EO damage the material?
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Compilation of Publications on
Ethyleneoxide in Paper
Conservation
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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, 21 - 25 April 1997, p. 193-203.
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 1998. 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, 12th Triennial Meeting Lyon, 29 August - 3 September 1999, Preprints Volume II, p. 550-554.
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. 507-512.
Christina Meier; Karin Petersen: Schimmelpilze auf Papier. Ein Handbuch fur Restauratoren, biologische Grundlagen, Erkennung, Behandlung und Pravention, Tonning [a. o.]: Der Andere Verlag, 2006
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
of ethylene oxide, Proceedings of the Educational Seminar, Washington DC, Health Industries
Manufacturers Association, 27-38, pp. 211-220, HIMA Report No. 80-4, 1980
Adkins B jr, Van Stee EW, Simmons JE, Eustis SL (1986) Oncogenic response of strain A/J mice to
inhaled chemicals. J Toxicol Environ Health 17: 311-322
AGS - Ausschuss fur Gefahrstoffe (2011): ERB (Exposition-Risiko-Beziehung)-Begrundung zu
Ethylenoxid (CAS-Nr.: 75-21-8). Begrundung zur ERB zu Ethylenoxid in BekGS 910.
ANAND, V.P., COGDILL, C.P., KLAUSNER, K.A., LISTER, L., BARBOLT, T., PAGE, B.F.J., URBANSKI, P., WOSS
CASIMIR, J., BOYCE, J. Reevaluation of ethylene oxide hemolysis and irritation potential, J. Biomed. Mater. Res.
64A, pp. 648-654, 2003
Alomar A, Camarasa JMG, Noguera J, Aspinolea F (1981) Ethylene oxide dermatitis. Contact
Dermatitis 7: 205-207
ATSDR –Agency of Toxic Substances and Disease Registry (1990) Toxicological Profile for Ethylene
Oxide- December 1990. CAS#: 75-21-8
Basketter, D.A., Griffiths, H.A., Wang, X.M., Wilhelm,. K.P., Mc Fadden, J. (1996) Individual, ethnic
and seasonal variability in irritant susceptibility of skin: the implications for a predictive human patch
test. Contact Dermatitis 35, 208-213;
Bokkers BG, Slob W. 2005. A comparision of ratio distributions based on the NOAEL and the
benchmark approach for subchronic-to-chronic extrapolation. Toxicological Sciences 85, 1033-1040
Bokkers BG, Slob W. 2007. Deriving a data-based interspecies assessment factor using the NOAEL and
the benchmark dose approach. Crit Rev Toxicol. 2007 37(5):355-73.
Bommer J, Barth HP, Wilhelms OH, Schindele H, Ritz E (1985). Anaphylactoid reactions in dialysis
patients: role of ethylene-oxide. Lancet 28:1382-1384.
Bruch CW. 1973. Factors determining choice of sterilizing procedure. In: Phillips GB, Miller WS, eds.
Industrial sterilization. Durham, NC: Duke University Press, 119-123.
(reviewed in ATSDR 1990)
CEN ISO/TS 11135-2:2008/AC:2009, Sterilization of health care products - Ethylene oxide - Part 2:
Guidance on the application of ISO 11135-1 (ISO/TS 11135-2:2008/Cor 1:2009)
Chapman J, Lee W, Youkilis E, Martis L (1986). Animal model for ethylene oxide (EtO) associated
hypersensitivity reactions. Trans Am Soc Artif Intern Organs 32:482485.
CICAD Concise International Chemical Assessment Document 54. Ethylene oxide. WHO 2003.
Csanady GA, Denk B, Putz C, Kreuzer PE, Kessler W, Baur C, Gargas ML, Filser JG (2000): A
Physiological Toxicokinetic Model for Exogenous and Endogenous Ethylene and Ethylene Oxide in
Rat, Mouse, and Human: Formation of 2-Hydroxyethyl Adducts with Hemoglobin and DNA.
Toxicology and Applied Pharmacology 165, 1–26 (2000)
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DFG –Deutsche Forschungsgemeinschaft (1984) Ethylenoxid. 1984.
DFG –Deutsche Forschungsgemeinschaft (1993) Ethylenoxid. 1993.
DFG –Deutsche Forschungsgemeinschaft (1996) Ethylenoxid Nachtrag 1996.
DFG –Deutsche Forschungsgemeinschaft (2002) Ethylenoxid MAK-Werte. 34. Lieferung.
DGAUM (2008) Toxische Gefahrdung durch Hautresorption; Deutsche Gesellschaft fur Arbeitsmedizin
und Umweltmedizin e.V. (DGAUM)
http://www.dgaum.de/index.php/publikationen/leitlinien/leitlinienarbeitsmedizin/251-leitliniearbeitsmedizintox-haut.html
Drager (2012) Analysenbericht 20121412, unpublished
Dunkelberg H (1982) Carcinogenicity of ethylene oxide and 1,2-propylene oxide upon intragastric
administration to rats. Brit J Cancer 46: 924-933
Dunkelberg H (1981) Carcinogenic activity of ethylene oxide and its reaction products 2chloroethanol, 2-bromoethanol, ethylene glycol and diethylene glycol. I. Carcinogenicity of ethylene
oxide in comparison with 1,2-propylene oxide after subcutaneous administration in mice. Zbl Bakt I,
Abt Orig B 174: 383-404
Dunkelberg H (1979) On the oncogenic activity of ethylene oxide and propylene oxide in mice. Brit J
Cancer 39: 588-589
ECETOC (1982) Technical Report Nr 5. Toxicity of Ethylene Oxide and its Relevance to Man. European
Chemical Industry, Brussels.
ECETOC (1982) Technical Report Nr 11. Toxicity of Ethylene Oxide and its Relevance to Man. An
updating of ECETOC Technical Report Nr 5. European Chemical Industry, Brussels.
ECETOC (1986) ECETOC document Nr 26 ECETOC statement on Ethylene Oxide toxicology and its
Relevance to Man. October 1986. European Chemical Industry, Brussels.
ECHA (2008): Guidance on information requirements and chemical safety assessment, Part E: Risk
Characterisation
http://echa.europa.eu/documents/10162/13632/information_requirements_part_e_en.pdf
ECHA (2009): Evaluation & Reporting of data: How to provide a (robust) study summary
http://echa.europa.eu/documents/10162/13566/evaluation_of_available_information_en.pdf
ECHA (2010a): Guidance on information requirements and chemical safety assessment, Chapter R 8 –
Characterisation of dose [concentration]-response for human health.
http://echa.europa.eu/documents/10162/13632/information_requirements_r8_en.pdf
ECHA (2010b): Guidance on information requirements and chemical safety assessment, Chapter R 19
– Uncertainty analysis,
http://echa.europa.eu/documents/10162/13632/information_requirements_r19_en.pdf
EMEA (2006) Committee for medicinal products for human use. Guideline on the Limits of Genotoxic
impurities. CPMP/SWP/5199/02.
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http://www.ema.europa.eu/docs/en_GB/document_library/Scientific_guideline/2009/09/WC500
002903.pdf
EN ISO 10993-7 (2009): Biological evaluation of medical devices Part 7: Ethylene oxide sterilization
residuals (ISO 10993-7:200 + Cor 1:2009) (consolidated version)
EU, (2008) SCHER/SCCP/SCENIHR (2008) Scientific opinion on use of the Threshold of Toxicological
Concern (TTC) Approach for the Safety Assessment of Chemical Substances. SCCP/1171/08
EU (2012) SCHER/SCCP/SCENIHR (2012) Scientific opinion on Toxicity and Assessment of Chemical
Mixtures. ISBN 978-92-79- DG for Health and Consumers. European Union.
European Chemicals Bureau (ECB) (2003) Technical Guidance Document on Risk Assessment.
EN ISO 11135-1:2007, Sterilization of health care products - Ethylene oxide - Part 1: Requirements for
development, validation and routine control of a sterilization process for medical devices (ISO 111351:2007)
Fennell T.R, Brown C.D. A Physiologically based Pharmacokinetic Model for Ethylene Oxide in Mouse,
Rat and Human. Toxicol. Appl. Pharmocology 173, 161-175, 2001.
Fluhr JW, Darlenski R, Angelova-Fischer I, Tsankov N, Basketter D. (2008) Skin Irritation and
Sensitization: Mechanisms and New Approaches for Risk Assessment. Skin Pharmacology and
Physiology 2008, 21: 124-135.
GESTIS Stoffdatenbank: www.dguv.de/ifa/stoffdatenbank
Ginsberg G., Foss B, Brown Dzubow R, Firestone M. Options for incorporating children´s inhaled dose
into human health risk assessment. Inhalation Toxicology 22(8): 627-647.
Graeter, L., Mortensen M.E. (1996) Kids are different: developmental variability in toxicology.
Toxicology , 111, 1–3, 15–20.
Grammer LC, Roberts M, Nicholls AJ, Platts MM, Patterson R (1984). IgE against ethylene oxidealtered
human serum albumin in patients who have had acute dialysis reactions. J Allergy Clin
Immunol 74:544-546.
Greaves-Walker WJ, Greeson CE (1932). The toxicity of ethylene oxide. J. Hygiene 32, 409.
Hallier E, Langhof T, Dannappel D, Leutbecher M, Schroder K, Goergens HW, Muller A, Bolt HM
(1993) Polymorphism of glutathione conjugation of methyl bromide, ethylene oxide and
dichloromethane in human blood: influence on the induction of sister chromatid exchange (SCE) in
lymphocytes. Arch Toxicol 67: 173-178
Hardt J., Schromer M.L., Angerer J. Untersuchung zur Exposition bei der Verwendung Ethylenoxidsterilisierter
Medizinprodukte im Krankenhaus. Arbeitsmed. Sozialmed. Umweltmed. 41, 5, 2006.
Hasegawa,R.; Hirata-Koizumi,M.; Dourson,M. L.; Parker,A.; Sweeney,L.M.; Nishikawa,A.; Yoshida; M.;
Report by Prof. Dr. habil. A. Strzelczyk Torun
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April – Aug. 1994
346,2 meter in total (261,2 m, 85 m in foulders, 13m notes)
The following measures were taken:
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1. sources of damage were analysed,
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The books were stored in wet/very humid conditions
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The books were dusty, there are spores in the dust, a risk for human health
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10 years ago (1984) the books were brought to dry rooms, but due to tight packing they dryed slowly
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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
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The humidity of the air in the room was between 57-62 % and the temperatureat 22,6 Centigrades
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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,
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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.
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4. the entire collection plus the 9 books and 15 groups of archival material was packed and prepared for desinfection
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Chamber for 20 m3, 10 kg Petrox, 5 days fumigation, then airwashing until EO detector did not show EO any more
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The rooms were desinfected with 2% Aseptin M solution and treatment repeated after 10 days
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5. Fumigation with 90% EO and 10% CO2 (Petrox gas)
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6. books were air washed and climatized,
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In Swidnica
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7. dust and microorganism spores were removed from the books in Sept. 1994 (after the report was written)
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8. the effectivity of the desinfection was evaluated (report Nov. 1994)
15 years later
2009 in Ossolineum
alle alten Drucke (Signaturgruppe SD) und
Handschriften (Signaturgruppe R)
begast worden.
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„2010 durch Adam Wilga, der eine solche Begasungskammer erfunden hat, die übrigen Bücher begast
(Signaturen 1,2,8000).“
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„Wenn es um die Signaturen geht, nach denen Sie gefragt haben, handelt es sich um fortlaufende Signaturen
(gemäß Katalog Dr. Górski).“
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Waiting for data from Ossolineum
MEN AND BOOKS - 2012
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 18th cent., 12 from 19th cent. Rest 20th 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 18th, 19th and 20th 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.
Books brought to Horn
off gasing measured
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 0 - 200 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 1612. 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/2003-154/pdfs/1612.pdf)
Umweltbundesamt
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Takes the influence via inhalation for the gratest
risk
Not so much touching
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.
Workflow Dummies
Dummy A 1
Nach der
Herstellung
direkt für
Ethylenoxidbe
gasung ohne
Zwischenschri
tte
Dummy A 2
Nach der
Herstellung direkt
für
Mikroorganismen
beimpfung ohne
Zwischenschritte
Dummy A 3
Dummy A 4
Nach der
Referenz
Herstellung direkt
für
Mikroorganismen
beimpfung ohne
Zwischenschritte
Dummy A 5
Nach der
Herstellung direkt
für Alterung
Dummy A 6
Nach der
Herstellung direkt
für Alterung
Dummy A7
Nach der
Herstellung direkt
für Alterung
Dummy 8
Nach der
Herstellung direkt
für Alterung
Dummy A 5
Dummy A 6
Dummy A 7
Dummy A8
Alterung
Referenz
Alterung Weiter
zur Ethylenoxid
begasung
Alterung
Weiter zur Mikro
Organismen
beimpfung
Alterung
Weiter zur Mikro
Organismen
beimpfung
Dummy A2
Dummy A3
Direkt vom ERC Direkt vom ERC
kommend zum kommend zum
Beimpfen
Beimpfen
Beiter zum
Ethylenoxid
begasen
Dummy A 7
Von der TU Graz
kommend zum
Beimpfen
Referenz
Dummy A 8
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
Suggestion book block for more volume
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!
Aims ERC took over in the project:
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- measuring off-gassing ethylene oxide
- evaluation of toxicity(Umweltbundesamt)
- provide dummies
- analysis of the parchment&leather
- interpretation of analyse-data
- 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
- suggestions of alternative methods to disinfect mouldy written/printed heritage
- disseminate the project results (website, journals, etc.)
- organise the joint exhibition in coop. with the other partners
- organise the final conference in coop. with P5.
- 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
& laymen, local newspapers, TV, radio, underlining the benefit of EU funding;
ERASMUS-students
- workshops beyond project runtime
Next steps
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Work flow Graz BOKU Ossolineum
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Shrinkage Temperature
Measurement
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Graz: Paper tests
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Umweltbundesamt Results
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BOKU results on fungi
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Question: is the paper more
disposed to new attack by the
ethylene Oxide treatment or not?
HW
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
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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