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Estimation of gelatin content in historical papers using NIR spectroscopy
National Archives and Records Administration
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J. B. Lang
University of Iowa, firstname.lastname@example.org
Getty Conservation Institute
Getty Conservation Institute
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Iowa City. Possible explanations for the decline are offered. and artworks printed from 1460-1791. . the means for all papers were quite high in the 15th century and dropped an average of 20% every 50 years. These values were combined with NIR spectra from the same papers to generate a model for predicting concentrations of unknowns. CA 90049 * Corresponding author mark. however. Los Angeles.ESTIMATION OF GELATIN CONTENT IN HISTORICAL PAPERS USING NIR SPECTROSCOPY Running title: NIR of gelatin in historical paper Note: This MS has been accepted with minor revisions for publication in e-Preservation Science. M. http://www.5 percentage points.0 and +1. In this project we developed a non-destructive method using near infrared (NIR) spectroscopy. T. The gelatin concentration in historical papers has never been well documented.6 and +1. 29 North Hall. University of Iowa. and M.morana-rtd. If a NIR measurement predicted a gelatin concentration in the range 0-6 percent then there is a 95% probability that the difference between the NIR model value and a destructive AA measurement would be between -1. IA 52242 3. We will provide a link to the final published version as soon as it is available. of Statistics and Actuarial Science. Barrett2.ormsby@nara. Ormsby1*. IA 52242 4.3 percentage points.gov ABSTRACT Gelatin sizing was a key ingredient during the handpapermaking era. J. Dept. 1200 Getty Center Drive. because measuring the gelatin content required destructive sampling.0 percentage points. The Getty Conservation Institute. Lang3. National Archives and Records Administration. Suite 700. Iowa City. Gelatin concentrations of 40 historical papers from the 15th-18th centuries were determined from amino acid (AA) concentrations by using gas chromatography/mass spectroscopy. Mazurek4. In a study of 159 specimens from books. College Park.B. 207 Schaeffer Hall. For 6-8 percent there is a 95% probability the difference would be between -2. MD 20740 2. and for 8-12 percent the difference is between -3. J. Room 1800. the online conservation science journal. loose leaves.com/epreservationscience/ Those revisions are in place but have not yet been approved by the editors of the journal.0 and +2. University of Iowa Center for the Book. 8601 Adelphi Road. Schilling4 1.
and Kolar et al. a common ingredient in papers made between the 15th and the 18th century. on the other. sizing. . Barrow also did not test for gelatin. Lang et al.10 In both cases. industrial method to quantify the glue in paper. Subsequent tests showed promising results with nearinfrared (NIR) spectroscopy. paper. found high copper contents in some historic inks. and increased gelatin and calcium content and higher pH. as demonstrated in research on the oxidation of sulfur dioxide in gelatin.7 They also documented the higher moisture holding capacity of a gelatin sized paper compared with an unsized control. but it also strengthened the paper. used this set of 35 papers to explore the use of attenuated total reflectance mid-infrared spectroscopy for this purpose. INTRODUCTION William Barrow’s 1974 study of 1500 bookpapers made between 1507 and 1949 was pioneering in its analysis of historical specimens to reveal new information about paper permanence and durability.6 Baty and Barrett confirmed gelatin’s anticipated ability to act as a pH buffer in paper. Dupont showed that gelatin has a significant role in reducing degradation induced by papermakers’ alum.4 Copper can also catalyze oxidative decay.Page 2 Ormsby et al. the accuracy of the non-destructive methods was less than desired.2 Several researchers have provided evidence that gelatin may promote paper stability. however. Kolbe demonstrated that gelatin can bind free iron(II) ions in unbalanced iron-gall inks that can catalyze oxidative degradation. include papers from the 1400s known to be exceptionally stable. the gelatin-sized papers also had more discoloration and lower pH after accelerated aging. Gelatin was added as a sizing agent to make the paper more resistant to ink bleeding.8 They found a relationship (although not a strong one) between lighter color on the one hand.11 These earlier studies led to the current project. The current project builds on Barrett and Mosier’s 1995 research which analyzed the gelatin concentration in a group of 35 historical papers using a destructive. although the net impact of this latter effect on paper permanence and durability is unknown. The resulting set of paper specimens with known gelatin content were set aside for use in the future development of non-destructive gelatin measurement techniques. near infrared spectroscopy 1.5 As with iron(II) ions.9 and other work on these same specimens used reflectance measurements. KEYWORDS: gelatin.1 His study did not.3 However. This was the only method future researchers could use to undertake a much broader study of 15th century papers in exceptional condition and compare them with papers made in subsequent centuries when paper quality declined. gelatin is able to bind copper.
13 Not only is this method difficult and time-consuming. EXPERIMENTAL Data were collected with an Analytical Spectral Devices LabSpec Pro UV/VIS/NIR spectrometer. As a result of these limitations. Of the 40 historical specimens. A Spectralon® (pressed polytetrafluoroethylene) disk was used as the white reflectance standard. particularly at the higher concentrations. Some specimens whose gelatin content was previously measured by the TAPPI method were selected to attempt to include a broad range of gelatin concentrations. A LabSpec Pro reflectance probe with a standoff reflectance accessory collected spectra over a circular area about 5 mm in diameter. The accessory holds the probe at approximately 70 degrees relative to the surface of the specimen. . Table I lists the specimens and their date of manufacture along with the analysis results. Spectra were gathered over a range of 350-2500 nm at 1 nm intervals. Preliminary tests were made by taking spectra with no support behind the sample area and then repeating the measurements with the specimen placed on a metal plate. gelatin concentration predictions based on these earlier models were less precise than desired. Developed by Schilling and Khanjian.14. The tests showed significant differences in absorbance between these spectra as a function of wavelength. In contrast to the TAPPI method. an AA present in gelatin. the GC/MS approach quantifies gelatin based on seven amino acids. not just the surface. but the results also suffered from large standard deviations. For the current project. 2. Used for conservation treatments. Grammage measurements were made on the air-dry (AD) specimens without preconditioning or conditioning. In earlier mid-IR and NIR work the models were calibrated using the gelatin concentrations determined by Barrett and Mosier in 1995. not just hydroxyproline.Page 3 Ormsby et al.12 The flexible sheet can be inserted between pages of a book to provide the background for collecting spectra. The system was calibrated at the beginning of each data collection period. 15 this method has been used extensively in paintings conservation for binding media analysis. To provide a uniform and consistent background the specimens were placed on top of a Gore-tex® sheet. with the probe lens approximately 4 cm from the document The accessory has a window which allows the specimen to be viewed and assists in positioning the probe. Preliminary tests indicated that room lights did not affect the spectra from specimens. a wet chemical procedure which measures the concentration of hydroxyproline. They employed Technical Association of the Pulp and Paper Industry (TAPPI) Method T504a. the sheet is a laminate of expanded polytetrafluoroethylene bonded to a non-woven polyester felt. indicating that the entire thickness of the sheet was being sampled. the gelatin concentrations in a new set of 40 historical specimens were measured by removing samples of paper and analyzing them as ethyl chloroformate derivatives using gas chromatography/mass spectroscopy (GC/MS). half were categorized as light and half as dark.
Vol.03 0.10 0.18 D1 T. Romans.” grammages were approximated due to voids from previously removed sample material. dev.03 . TB UI Coll. Opera Omnia ad Jus Ponfificum spectantia. Poems on Several Subjects. II./USA 66 61 0. The History of English Poetry TB UI Coll. Warton.10 3. Annals of 1764 1608 1695 1769 1772 London Monguntiae Amsterdam London London 86 54 104 76 94 1749 1734 1645 Paris London Geneva 77 68 59 3. WB 1484 D3 P. Arca medica variis divinae scripturae.73 2. TB = Barrett ID number from previous research or other identification information.13 0. WB 1382 D9 A. Oratio in Funere TB UI Coll. Note: Some attributions require additional research/clarification. De Feudis libri sex. Busaeus.04 1695 1778 Strasbourg Conn. Percival.15 0.84 0. Table I: Historical specimens used to develop NIR model Historical Specimens with weight percent gelatin based on 7 AA concentrations as determined by GC/MS.02 std.12 0. Essays Medical and Experimental. Cains) D4 J. WB = William Barrow Laboratory ID number. Gregorie. D5 T. Espinosa) D7 Bishop Burnet’s history. (from T.13 1. WB 1269 D10 B. TB W35. TB UI Coll.14 3. Francii.25 3.31 0. D2 J. D6 De Convulsionibus. WB 1170 D8 P. TB UI Coll.Page 4 Ormsby et al. Ogilvie. ID # ID Year City or Country Grams/ Meter2 Gelatin % w/w (average of 3) 1. Mincucci. of gelatin % w/w 0.36 0.14 0.01 0.11 0. (from R. “Est.
WB 1052 The law of the covenants. Plutarchi….2. (from R.94 0. BMLV 180.17 0. WB 1187 Monsieur l’Abbe. TB P72.54 3.22 2. WB 1512 Biblia Latina. Nicolaus Jenson. P. the troubles in the Netherlands.17 0.10 0. Specimen 18 D11 D12 D13 1711 1757 1739 Savoy unknown London 59 75 76 1.39 0.98 0. Joannis Nider Ordinis Praedicatorum Theologi De Reformatione Religiosorum. V. Reports of cases.08 L1 L2 L3 1479 1503 1770? Venice ? Spain 91 85 81 4. WB 1158 J.54 6.1. Roman History James McBey Collection of Watermarked Paper. Goff B563 Blondus.89 1. WB 1019 H.68 0.44 4.93 . Kt. TB T91. Espinosa) R. “Printed in London.15 0. 1739” TB UI Coll. Patri) Feltwell. WB 1214 Unprinted leaf watermarked “1757” (from S. Histoire des guerres civiles. F.Page 5 Ormsby et al.10 D15 D16 D17 D18 D19 1733 1793 1584 1727 1757 Edinburgh London Basel Savoy Amsterdam 71 81 73 83 98 1. Wolf.07 0.26 0. In Ciceronis Officia.86 0.quae exstant omnia.22 0. WB 1523 The eleventh part of the reports Sir Edward Coke. 1. V.45 D20 1599 Frankfurt 71 0.37 1. WB 1452 The humble and modest inquiry.01 3.22 0. Angelum Britannici Press. Burrow. TB T99. TB 45.39 D14 1611 Antwerp 80 4. V. TB P97.66 8. WB 1101 Plutarch.
18 5.07 0.76 0.35 0.02 4. Paterculix Que Supersunt: WB 1208 Bible. TB G15 Jean de Charlier de Gerson.98 0. WB 1340 James McBey 1723 1737 1498 1495 London London Venice Rome 72 98 96 88 3.76 0.19 0.56 L16 1660 London 83 4.55 4. D’inghilterra tra le due cafe di lancaftro e iorc. UI SC PL duplicate Horatius Flaccus.38 L14 1641 Venice 109 3. Edward Coke Knight. Biondi. TB UI Coll.Page 6 Ormsby et al.16 L17 1700s ? 89 4. (from R. Silber. 2. Historium AB Inclinatione. L4 L5 L6 L7 Anno Regni Georgii Regis (from R. Velleii.44 4. L’istoria delleverrecivili.71 0.78 11.52 L10 R L11 R L12 L13 1711 1477 1482 1400s Oxford? Augsburg Florence Italian? 78 103 80 est. WB 1379 A narrative of the proceedings of the lower house of convocation. Scotus M. Espinosa) F.83 0.04 0.14 L15 1701 London 66 6.58 L8 L9 1488 1483 Strasbourg Venice 81 100 8. Guintus Opera. Politanus Opera. TB 146. (In German). Zainer. Flavius. TB G14 Blank leave with three hills watermark TB G17. Printed by E. Aldus.36 0. 81 est.71 0.24 2.57 0. TB T2. TB T165.90 1.15 . TB UI SC Griffin Blondus. Lieberman) The Muses Library. UI SC PL Johannes Antonius Campnus Opera.38 1. WB 1239 The fifth part of the reports of Sr.07 7. Goff G186. Printed by O. or a series of English Poetry.
Areas with ink or stains were avoided. and the reflectance probe and fiber optic connections were disassembled. a second set of 20 spectra was gathered on another day.2 mm in diameter from 10 locations distributed over each specimen.Page 7 Ormsby et al. The same procedure was followed for a third session.37 For the AA analysis. TB G/T16 The history of the reign of Henry the Fifth.53 0. TB T25 Antonius De Bitonto.22 L19 L20 1704 1483 London Venice 79 87 3. Collection of Watermarked Paper.84 0. Specimen 32. TB T3. Material was punched equally from the 10 different locations sufficient to generate 3 samples of 5 mg each AD weight as was required for triplicate GC/MS analyses. Johannes Capreolus Defensionum Theologia. so a total of 60 spectra were gathered from each specimen. Aquinatis. WB 1245 T. Sermones Quadragesimale De Vitiis. Between sessions the system was powered down.43 6. To study the repeatability of the measurements and simulate use in the field. a Whatman Harris micropunch was used to remove circular samples 1. Figure 1 shows the average of these 60 spectra for each of the 40 historic specimens. so a total of 20 spectra were gathered from a specimen during a given data collection session. Figure 1: Spectra from 40 historic specimens . TB G/T12 L18 1499 Venice 75 10.43 0. NIR spectra were taken as close as possible to the 10 sampling locations on each specimen. Data were collected on both sides of the sheet.
The specimens were stored in the room between analysis sessions. Based on the prediction residual error sum of squares plot and F-ratio values. Figure 2: Response of specimen to changing RH 3. museums. To study the effect of this variable. a few specimens were placed in desiccators at 20-25% RH and allowed to equilibrate for at least one day. immediately placed on the sampling stage.16 a model was selected utilizing four factors and the wavelength ranges highlighted in blue in Figure 3. and analyzed by collecting spectra at 10-15 second intervals over the next 10-15 minutes as the paper responded to the ambient environment of 50-55% RH. A specimen was then removed. first derivative of these spectra calculated using the gap method with spacing 15. RESULTS The averaged spectra from the 40 specimens and the gelatin concentrations determined by the GC/MS method were analyzed with Grams/PLSplus IQ chemometric software. The region near 1900-2000 nm was excluded in an attempt to reduce sensitivity to differences in moisture content caused by variations in RH when the equipment is used in the field. The model used partial least squares with leave one-out cross-validation.Page 8 Ormsby et al. . These spectra were collected with the instrument in an environmentally-controlled room with temperature 22° C and relative humidity (RH) 50-58%. When the instrument is used in the field in archives. libraries. and other environments. In future work it might be possible to incorporate the response as a function of RH into the model and to predict the moisture content of the specimen. the RH may vary considerably. Figure 3 shows the mean centered. Figure 2 shows a typical result with the greatest response in the range 1900-2000 nm.
. Missori et al. those wavelengths were not added because of the wide scatter of the first derivative spectra (Figure 3).74. 17 and it was expected that including the UV-VIS range would enhance the model. and the vertical axis is the percent gelatin as predicted by the cross-validated NIR model. Figure 3: Processing of spectra to develop model The UV and visible ranges were not used because various tests indicated that they introduced more noise without improving the model. To take advantage of the information contained in the UV-VIS range it would be helpful to have a larger set of historical specimens and perhaps to try different chemometric analysis methods. The error bars show one standard deviation calculated from the triplicate GC/MS measurements. The horizontal axis is the percent by weight of gelatin as measured by the destructive GC/MS AA analysis. .Page 9 Ormsby et al. The standard error of cross validation16 (SECV) was 0. used 96 papers from the 17th to the 19th century and employed a genetic algorithm to develop the chemometric model. The relatively poor sensitivity of the system in the UV range may explain the results in that region. For example.18 Figure 4 shows the results of the new model using the 40 specimens. demonstrated the effects of gelatin sizing on the reflectance of paper. While including portions of the visible range may have improved the model marginally. Cséfalvayová et al.
. Above 6% the standard deviations are comparable. The average of each set of 10 was calculated for all 3 sessions. For this study. That is. These averaged spectra yielded 6 gelatin predictions. For the majority of specimens with gelatin concentrations below 6%. Figure 4: Predicted vs. As is clear from Figure 5 and discussed further below. this approximation is less accurate at higher concentrations (8% and above). which are illustrated by the horizontal error bars in Figure 4. the size of the reference value uncertainty was evaluated compared to the standard deviation of the NIR predictions. Various methods have been proposed for incorporating reference value uncertainties into the chemometric modeling process. and the accuracy of the model could be improved by adding more calibration specimens in this range. the standard deviation of the NIR prediction is significantly larger than the standard deviation of the AA measurement. Future work could also incorporate the techniques discussed in references 19-21. actual comparison While the R-squared and SECV values give some indication of how well the NIR model fits the calibration data. the uncertainties in the AA values are assumed to be negligible relative to the standard deviation of the NIR readings. with a few exceptions. yielding 6 spectra per specimen. these quantities do not take into account the uncertainties in the AA measurements. Figure 5 compares the size of standard deviation of these 6 NIR predictions with the standard deviation of the AA measurements. Overall. As discussed above.19-21 and the topic is under active development in the field.Page 10 Ormsby et al. in developing the model 10 spectra were collected from both sides of a reference specimen during a given data collection session. the standard deviation of the replicate NIR readings is a reasonable approximation of the uncertainty in the gelatin prediction.
Figure 5. if the NIR measurement on a specimen predicted a gelatin concentration in the range 0 to 6 percent then there is a 95% probability that the difference between the NIR model value and a destructive AA measurement would be between -1. but for clarity the vertical axis shows the difference between the concentration predicted by the NIR model and the GC/MS AA measurement.0 percentage points. . but all replicate predictions are shown instead of the average. Comparison of standard deviation of replicate NIR measurements and AA data The data from Figure 4 are re-plotted in Figure 6. Again.5 percentage points.3 percent. Between 6 and 8 percent gelatin there is a 95% probability the difference between the two measurements will be between -2.3 percentage points.Page 11 Ormsby et al.0 and +2. and between 8 and 12 percent the difference is between -3. The outer lines are the 95% prediction intervals based on the repeatability of the measurements. Based on these results. there is about a 95% chance the AA measurement would be between 3. For example.0 and +1.0. the outer lines are the 95% prediction intervals.6 and +1. if the NIR value was 5. Figure 7 illustrates the same data.4 and 6. We found no statistically significant difference in the gelatin concentration on the front versus the back of the specimens.
Page 12 Ormsby et al. To address this issue. In addition. In future work we hope to refine the model by including more specimens at the upper levels. preliminary studies were made using a combustion analysis technique on the papers to . These difficulties may account for the wider error bars on some points at higher levels in Figure 4 (although the relative standard deviation of these points is comparable to that at lower levels). at higher concentrations there may be limitations in the water extraction procedure used to quantitatively extract the gelatin from the paper for subsequent AA analysis. Figure 6: Data from repeatability tests Figure 7: Difference between model and AA results At the higher concentrations the model is less accurate in part because there are fewer calibration points in this range.
5% on the vertical gelatin scale. The gelatin content was calculated by the model using this average spectrum. but the conclusions about changes over time would not be altered. The black dashed lines give the 95% confidence intervals for the means. avoid the need for water extraction of the gelatin. the 86 papers from 1460 to 1499 were in excellent condition. loose leaves. On each specimen 8 spectra were collected and then averaged.22 Based on this model. The 73 papers made after 1500 were in a range of condition from excellent to poor. the placement of all data points and trend lines would shift upward 0. With 95% confidence. The results are shown in Figure 8 where the gelatin concentration is plotted versus the year of printing. Unfortunately. and works of art printed between 1460 and 1791. With few exceptions. NIR scans of these specimens were collected with an Analytical Spectral Devices QualitySpec Pro UV/VIS/NIR spectrophotometer. This instrument is identical to the LabSpec Pro instrument used for the modeling study except for the LabSpec Pro’s optional batterypowered operation for use in the field.5 in the gelatin prediction was found. The model discussed above was used to study the gelatin content of 159 specimens selected from books. The computations were carried out using the “glm()” function in the R software language.4%.5 correction. The blue line gives the maximum likelihood estimates of the means based on a log-linear Normal errors model. If a correction was applied to the original data shown in Figure 8. Subsequent testing following this work factored in the 0. plausible values for this 50 year drop are between 16. an offset of 0.6% and 23. inconsistent agreement with the AA-derived data suggested that some specimens had nitrogencontaining compounds other than gelatin present. During tests of agreement between the instruments using reference specimens. the mean gelatin content for all papers tested dropped an average of 20% every 50 years.Page 13 Ormsby et al. Figure 8: Gelatin concentration over time . Nitrogen values obtained using this method were used to calculate percent gelatin values.
Why would this be the case? One possible explanation is that European paper made prior to 1500 was designed to imitate parchment in its writing. A total of over 1. but an entirely different and cheaper material in its own right.23 Bookbinders may have gone to the trouble of this added step because the paper was otherwise too weak to withstand binding and end use by readers.500 specimens will be analyzed using NIR as well as x-ray fluorescence methods. Figure 8 represents data on only 159 items. which coincides with the widely observed overall decline in paper quality. Other researchers have also demonstrated that NIR has great potential for non-destructive analysis of paper.18 may also improve the model. an analysis of a much larger sample group is required. Regardless of who applied the gelatin to the paper. 4. Such a survey is now underway as a result of the development of this technique and a recent grant from the Institute for Museum and Library Services Conservation Support Program. such as used by Cséfalvayová et al. Therefore. handling and working properties. We are also investigating using the full UV-VIS-NIR range of the spectra gathered with this instrumentation to measure relative differences in paper color and to predict certain strength characteristics. we hope to refine the NIR gelatin model by obtaining more calibration points at the higher concentrations (8 percent and above) where it is less accurate. both handmade historic specimens and more modern machine-made .Page 14 Ormsby et al. around 1500 there was also likely a changing perception that paper was no longer a substitute for parchment. In order to be more confident that the apparent decline in gelatin concentration is representative of what actually happened between the 15th and the 18th centuries. DISCUSSION It appears that the gelatin concentration in paper dropped significantly after 1500. Advanced chemometrics techniques. Szirmai argues that by the late 15th century.. fairly heavy gelatin sizing likely persisted into the end of the 15th century out of tradition. In addition. possibly due to requests from the printers to decrease sizing amounts to ease their dampening work before printing. With the rapid spread of printing. But after 1500 things changed quickly. papermakers were in fact supplying unsized paper to the printers. sizing concentration dropped off. The only way to achieve these characteristics in paper made from old linen and hempen rags was with high levels of gelatin sizing. The resulting decrease in size required would have been welcomed by the papermaker due to the reduction in work and expense. and it was the binders who applied the size later.
7. Timothy Barrett Principal Investigator. J. W. Kress Foundation. Vol. Barrett. REFERENCES 1. Barrow Research Laboratory. A small scale survey using this method showed a significant decrease in the concentration of gelatin after the start of the 16th century. Inc. Permanence/durability of the book. 1989. degree of polymerization. This research was funded in part by an Institute for Museum and Library Services Conservation Project Support (Research) Grant to the University of Iowa Museum of Art. and other properties as part of the SurveNIR project. Inc.500 specimens dating from 1650 to 1990. Virginia. ACKNOWLEDGEMENTS We thank the following organizations for their support for this research: The Samuel J. Strlic et al. and in subsequent testing of unknowns we were able to document very high gelatin concentrations in papers made before 1500.24 Because our focus was on the gelatin content.” May 2007. Richmond. 5. papers.. 13. particularly at the higher concentration ranges. . 1974. Vol. Compared to our earlier efforts. Analytical Spectral Devices. T. Physical and chemical properties of book papers 1507–1949. our calibration set included the mid 15th to the mid 17th century period. the National Archives and Records Administration Preservation Programs. the current approach is more accurate.. W.Page 15 Ormsby et al. Barrow Research Laboratory. CONCLUSIONS This study has demonstrated that NIR chemometric modeling can be used to nondestructively measure the gelatin content of historic paper specimens. lignin content. and the Getty Conservation Institute. developed chemometric models for gelatin. The Paper Conservator. Project Title “Analysis of 15th-19th Century Papers Using Non-destructive Techniques. 2. pH. Early European Papers/Contemporary Conservation Papers. J. in part because of the better calibration data provided by the GC/MS analysis of AAs. the University of Iowa Office of the Vice President for Research. Future efforts will expand this survey and also aim to refine the model to more accurately predict gelatin concentration. By using a very large calibration set of over 1.
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