18th-Century Glue Recipes: Towards Identifying Glue Residues from

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Chapter 6

18th-Century Glue Recipes: Towards Identifying Glue Residues from Ferry Farm, George Washington’s Boyhood Home Daniel Fraser,*,1 Mara Kaktins,2 and Ruth Ann Armitage3 1Department

of Chemistry and Physical Sciences, Lourdes University, Sylvania, Ohio 43560 2George Washington Foundation, Fredericksburg, Virginia 22405 3Department of Chemistry, Eastern Michigan University, Ypsilanti, Michigan 48197 *E-mail: [email protected]

Archaeological investigations at Ferry Farm, home to the Washington family from 1738−1772, have yielded numerous ceramic artifacts associated with Mary Washington, George Washington’s mother. Several of these bear residues of historic mending. The nature of the glues, and the relationship between these various artifacts, remains poorly understood. We are using direct analysis in real time mass spectrometry to investigate the composition of three classes of replica historic glues made from hide, resin, and milk/cheese. Based on these results, we sought to characterize the historic glue residues to provide insight into the practice of china mending in the 18th century.

Introduction Ferry Farm, located across the Rappahannock River from Fredericksburg, Virginia, was the boyhood home of George Washington. The Washington family lived at the Farm from 1738-1772, occupying the second of five houses to be built at the site. The house was reportedly damaged by fire on Christmas Eve, 1740. It was repaired and occupied by the Washington family until 1772, at which point Mary Washington moved to Fredericksburg. Presumably the house was in decline by the end of the 18th/early 19th century. By 1833 artist John Gadsby Chapman painted the landscape of Washington’s boyhood, depicting only a ruin where the © 2013 American Chemical Society In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


house once stood. This foundation was further damaged by Union soldiers during the Civil War who denuded the landscape and put a trench through the foundation of the Washington house (1) Intensive archaeological investigations at Ferry Farm have been ongoing since 2001. More than 500,000 artifacts have been excavated during this time, and the location of the original Washington house has been identified. Amongst the large collection of excavated materials were several ceramic sherds from Mary Washington’s collection of tea and tablewares. Examination of one of Mary Washington’s more elaborate tablewares, a creamware punch bowl with an enameled floral motif accented with cherries (Figure 1), revealed the presence of eighteenth century glue residues. Sherds from this punch bowl were recovered from the Washington house cellar. The hand-painted designs and distinct vertical crazing is similar to vessels attributed to the Cockpit Hill potters of Derby, England (2). It would initially appear as though the bowl was broken into at least four different fragments and subsequently glued together before a presumed second breakage episode and eventual discard. The glue residue can be seen as a light brown substance adhering to the broken edges of the vessel and aligning along “seams” where the bowl was broken previously. Figure 2 illustrates a cross-section of the bowl’s interior with glue extending across multiple adjacent sherds along the entire base. It should be noted that prior to our recognition of these residues, the historic glue was durable enough to survive washing by lab technicians unaware of the adhesives present. Microscopic examination confirms that the residues are not simply organic deposits which often accumulate on archaeological ceramics, although deposits of this nature are not common in materials excavated at Ferry Farm.

Figure 1. Mary Washington’s enameled creamware punchbowl with floral and cherry motif. Courtesy of George Washington Foundation. 110 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Figure 2. Glue residue adhering to the base of the punchbowl. Courtesy of George Washington Foundation.

To date, at least four additional vessels associated with the Washington family have been found to also exhibit glue residues along the broken edges. These include a creamware platter and plate, both with Royal Pattern rims, an enameled creamware lid, probably from a teapot, and a fragment of a porcelain hollowware with Imari palette. Additionally, two wig curlers recovered from the site also feature an adhering substance that bears some resemblance to the glue residues on the tablewares. Each has a seemingly identical application which runs the length of the curler on one side only, as though they were glued to another object, or possibly each other. While repairing broken ceramics is a practice that continues to this day, an explanation for why glue would be present on wig curlers has thus far eluded us. The discovery of these residues has prompted several questions: Are the same glues present on all of the sherds? What are the compositions of the glues? Were the mended vessels functional after their repair or used only for display? Was the mending done professionally or by a resident on the property? These questions led to undertaking some experimental archaeology to replicate and test the efficacy of 18th- and 19th-century home glue recipes and to the chemical analysis reported here. Glues and adhesives are found on archaeological materials as early as the Paleolithic period, where bitumen (3, 4) and birch bark tars (5) were used in hafting stone points. Birch bark tar was widely used in Europe, as a hafting material in Mesolithic Britain (6), and has been used to repair ceramics across Europe since the Neolithic (7, 8) and in Roman Britain (9). Some of these birch bark tar glues also contained beeswax (7). Others have observed mixtures of pine resins or birch bark tar and beeswax or animal fat in archaeological adhesives (10–13). Pine resins, possibly processed into a glue for hafting or repairs, have been identified on a ceramic sherd from the Western Great Basin (14). Proteinaceous glues are water 111 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


soluble, and thus are unlikely to survive for long in the archaeological record. Two exceptions worth noting are the use of a proteinaceous animal glue in the construction of a terracotta horse from Qingzhou, China (15) and of an Egyptian cartonnage mummy case from the 22nd Dynasty (16). Most evidence for such glues is found in artists’ materials, where they are well preserved and appear as both adhesives and binding media in paints. Identification of characteristic compounds in glues – steranes, terpenes, waxes, amino acids – by mass spectrometry provides more specificity in analysis than does spectroscopic analysis (e.g., FT-IR). Gas chromatography-mass spectrometry (GC-MS) is the primary method for identifying di- and triterpenoids, lipids, and waxes in archaeological glues (e.g., 7-9). Extraction and derivatization is necessary for GC-MS studies, except when sufficiently volatile components can be collected from the headspace of a glue or whole artifact using solid-phase microextraction (17). For proteinaceous glues, hydrolysis – for up to 24 hr – is necessary to reduce the protein to amino acids, and derivatization must also be carried out for GC-MS (18). Identification of species-specific peptides may also be undertaken by mass spectrometry, though this area of research remains somewhat in its infancy (19, 20). Pyrolysis GC-MS, with or without on-line hydrolysis/methylation, eliminates the need for lengthy sample preparations, though separation still requires significant amounts of time. Direct inlet mass spectrometry of archaeological glues (21, 22) has been reported as a fast, simple identification method, though the extensive fragmentation and overlap of ions makes interpretation of the complex spectra a significant undertaking. Such an analysis without fragmentation that is able to clearly differentiate between sources of glues without sample preparation would be ideal. Ambient ionization methods like desorption electrospray ionization (DESI) and direct analysis in real time (DART) are capable of rapid, simple mass spectrometric analysis of intact proteins and small molecules alike (23, 24). Such applications have great potential for archaeological materials (25, 26). We report here on applying DART with high resolution time-of-flight mass spectrometry to characterizing the glue residues from Ferry Farm, and comparing their composition to replica glues based on period recipes.

Methods and Materials Experimental Archaeology One of us (MK) and Melanie Marquis, Archaeological Laboratory Supervisor, replicated three basic glue types from period literature that may have been used at Ferry Farm in the 18th century: resin glues, hide glues, and cheese glues (27–29). Because it seemed unlikely that the wig curlers had been repaired, we replicated an 18th-century recipe for a pomade that would have been used to set wigs on such curlers. The ingredients in the replica glues and pomade are provided in Table I. A sample of pitch obtained by heating birch bark in an oxygen-free environment was also prepared for comparison to the historic glues. To determine how well the glues performed, each of the replica glues was used to repair modern ceramic objects with pastes similar to those of 18th-century 112 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


wares. The glues were evaluated for their ease of application, adhesive properties, and post-depositional change. Hide glue was simple to apply thinly with a brush and made nearly imperceptible repairs, but it decomposed almost completely during six months of burial on site. The cheese and resin glues were both difficult to apply and the repairs were not suitable for either future use or display. The resin glue was significantly altered by burial, darkening perceptibly and becoming brittle and flaky. The cheese glues appeared to survive best, bonding tightly to the ceramic paste and changing color slightly. These glues appear to be the most likely of the three replica glues to survive archaeologically.

Table I. Replica 18th- and 19th-century glues prepared for this study Glue name

Ingredients

Hide glue 1

Hide/sinew glue, isinglass, brandy, pickling lime

Hide glue 2

Hide/sinew glue, white vinegar, garlic, ox gall, pine resin, turpentine, sandarac, gum mastic, brandy

Cheese glues 1 and 2

White vinegar, whole milk, pickling lime, egg white

Cheese glue 2A

Grated cheese, pickling lime, egg white

Resin glue

Pine tar resin, beeswax, pickling lime

Birch bark pitch

Pitch prepared from heating birch bark in the absence of air

Pomatum

Beef bone marrow, hazelnut oil, lemon oil

Table II. Authentic 18th-century glue samples submitted for analysis Description

Ferry Farm ID number FF-12-100-161 (a)

Punchbowl footring

FF-12-100-161 (b)

Creamware plate bottom w/ Marley

FF-10-273-22

Imari

FF-12-411-2

Creamware tea lid

FF-12-100-161

Creamware platter

FF-10-273-17

Wig curler 1 (broken)

FF-10-254-2

Wig curler 2 (complete)

113 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Samples for Analysis Samples of the replica glues described in Table I were sent to EMU for characterization by direct analysis in real time time-of-flight mass spectrometry. Fragments of glues from Mary Washington’s ceramics and the residues from the wig curlers were removed using scalpels, placed into clean glass vials and sent to EMU for analysis as well (Table II). Additional samples of the cheese and resin glues after six months of burial were also analyzed, along with samples of the soil from both the reproduction burials and the Washington house cellar from which the authentic ceramics were excavated. The glue samples – both replica and authentic – were analyzed both as received and as hydrolysates by direct analysis in real time time-of-flight mass spectrometry. Hydrolysis was carried out to determine the amino acid content of the glues, which would differentiate hide glues from the other recipes based on the high concentration of hydroxyproline relative to other amino acids from collagen. A few micrograms of each sample and 20 μL of BOC-bromophenylalanine as internal standard (0.2 mg/mL) was placed into a reaction vial with 40 μL 6 M hydrochloric acid, purged with nitrogen, sealed with a teflon septum and cap, and heated to 120 °C for 60 min in a heating block. A control sample with only internal standard and HCl was prepared in the same manner. After cooling, the resulting solution was subjected to DART-MS analysis on the closed end of a melting point capillary tube. DART-MS Analysis The hydrolysate solution, glue powder or fragment was simply held in the gap between Orifice 1 of the AccuToF mass spectrometer (JEOL USA, Peabody MA) and the DART ionization source (IonSense, Saugus, MA). The DART was used in both positive and negative ionization modes with helium at 350°C. Orifice 1 was set to 30V to minimize fragmentation and 120°C; Orifice 2 was held at 5V, and the ring lens voltage at 5V. The DART grid voltage was kept at the default values of +240V and -530V. The mass spectrometer RF ion guide (“peaks voltage”) was set to 700V to maximize sensitivity in the low mass range to include all of the amino acids. Mass calibration was carried out using PEG-600 in methanol during each acquisition. The mass resolving power was approximately 6000 (as calculated by m/Δm).

Results and Discussion Replica Glues: Hydrolysis While amino acids can be detected using DART-MS in either positive ion mode (as MH+ ions) or in negative ion mode (usually as M-H- ions), negative ion mode has better sensitivity. This was confirmed in our analyses when the internal standard could not be detected at all in positive ion mode in some of the samples, yet was readily observed in negative ion mode. The results for amino acids and fatty acids are reported here for negative ion mode. The control hydrolysate sample 114 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


contained no significant quantities of amino acids, though traces of asparagine (Asn), glutamine (Gln), and glutamic acid (Glu) were observed. High resolution mass spectra of the hydrolysates of the replica glues showed that the three general types of glues differed greatly in amino acid content. Hydroxyproline (Hpro) (C5H9NO3, M-H- m/z 130.050) was readily distinguishable from leucine/isoleucine (Leu/Ile) (C6H13NO2, M-H- m/z 130.087) at high resolution, eliminating the need to chromatographically separate the amino acids for analysis. Hide glues 1 and 2 contained significant quantities of hydroxyproline, as expected. The cheese glues surprisingly contained few or no amino acids; however, it was also observed that little of the internal standard was recovered from the cheese glue samples. The high proportions of pickling lime in the cheese glues may have neutralized a significant amount of the acid, leading to a lower yield of amino acids in the hydrolysate. Two saturated fatty acids – palmitic (hexadecanoic) acid and stearic (octadecanoic) acid – and their monounsaturated counterparts were present in significant quantities. These fatty acids are the dominant lipids used as evidence of dairy products in archaeological materials, though their presence can be attributed to numerous fat-containing substances as well. The resin glue contained a tiny amount of both Asn and Gln, but no other amino or fatty acids. The mass spectrum for the hydrolysate of the resin glue was dominated by a peak at m/z 299.195, indicating the presence of significant quantities of dehydroabietic acid (C20H28O2, Figure 3). Abietic acid (C20H30O2), a marker compound for pine resin, was also present at m/z 301.210, as were numerous other oxidation products (15-hydroxy-7-oxodehydroabietic acid, 3,15-dihydroxydehydroabietic acid, etc.). The replica pomatum contained small amounts of all of the amino acids except cysteine (Cys), HPro, Glu, methionine (Met), histidine (His), and tyrosine (Tyr). The spectrum for the pomatum hydrolysate was dominated by the saturated fatty acids. The birch bark pitch was not hydrolyzed for this study. Replica Glues: Direct Analysis Direct analysis of the replica glues required no sample preparation: subsamples of the material were simply held in the ion source. This was useful in that it revealed the presence of a large number of different compounds. For simplicity sake, we focus here on two groups of compounds that differentiated the glue recipes for which amino acids were unhelpful. For the cheese glues, this meant looking at the fatty acid composition, while for the resin glue and birch bark pitch, we considered characteristic marker compounds including abietic acid and lupenone. Birch bark pitch has been well characterized in archaeological contexts, as discussed in the Introduction. While there are many characteristic compounds in birch bark pitch besides lupenone and betulinic acid (Figure 3), only those compounds were readily identified in positive ion mode for the birch bark pitch prepared for this study. The even-chain fatty acids observed by positive ion direct mass spectrometry of the replica glues are summarized in Table III. Hide glue #1 may have been contaminated, as palmitic and stearic acids were both observed along with the monounsaturated C16:1 and C18:1 fatty acids. Hide glue #2 showed no evidence 115 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


of fatty acids. The cheese glues contained butanoic acid, and palmitic acid, as well as other fatty acids. The resin glue was devoid of fatty acids. As expected, the mass spectrum of the pomatum was dominated by fatty acids.

Figure 3. Structures for some of the compounds observed in pine resin and birch bark pitch. 116 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.

Table III. Saturated and monounsaturated fatty acid composition of replica glues. Number denotes the length of the carbon chain in the saturated and degrees of unsaturation (where applicable). Replica glue

4

6

8

10

10:1

12

14

Hide glue (recipe 1)

16

16:1

x

x

18 x

18:1 x


Hide glue (recipe 2) Cheese glue (recipe 1)

x

x

Cheese glue (recipe 2)

x

x

Cheese glue (recipe 2a)

x

x x

x

x

x

x

x

Resin glue Pomatum

x

x

x x

x

x

x

x

x

Hide glue #2 contained both pine resin and mastic in the recipe, which contributed abietic acid and oxidation products as well as several of the acids from mastic (oleanonic/moronic/masticadienoic/isomasticadienoic acids, all C30H46O3). The resin glue mass spectrum was dominated by abietic and dehydroabietic acid and other oxidation products. The birch bark pitch was complex, containing the mastic acid and pine resin compounds in addition to the expected betulinic acid and lupenone. The reason for the presence of these other compounds remains unclear. No resin compounds were observed in any of the other glue recipes or the pomatum. Replica Glues After Burial Because the replica hide glues decomposed almost completely within the six months during which it was buried, no sample was available for analysis. Samples of the cheese glues and resin glue after six months buried on site were examined using DART-MS. Only the direct analysis of the buried glues has been completed so far. Even after six months, the fatty acid composition of the cheese glue remained unchanged. The resin glue did not acquire any fatty acids from the burial environment, as its composition was also unchanged. The cheese glues did not contain any resin compounds after burial. Resin glue after burial also contained abietic and dehydroabietic acids, as well as 7-oxodehydroabietic acid. For comparison, samples of soil from the context in which the replica glues were buried were also examined with DART-MS. This soil showed no evidence of resin compounds and only traces of a few of the fatty acids (C4:0, C10:1, C16:0, and C18:1). 117 In Archaeological Chemistry VIII; Armitage, R., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.


Authentic 18th-Century Glue Residues Hydrolysates from the authentic glue samples described in Table II showed little evidence of amino acids. Only the glue from the footring of the punchbowl showed small amounts of serine (Ser), threonine (Thr), and tryptophan (Trp). Asn and Gln were both observed in nearly all of the samples, including the control hydrolysate, indicating some contamination in the sample preparation process. No hydroxyproline was observed in any of the hydrolysates of the authentic glues. Considering that the replica hide glues prepared from contemporary recipes did not survive even six months of burial, it appears unlikely that the authentic glues were prepared primarily from hide. Direct analysis of the authentic glue residues revealed the presence of phthalates in some of the samples, and dominated the spectrum of the glue from the Imari porcelain. All of the glue residues contained both C4:0 and C10:1, as well as other small even-chain fatty acids in the range from C4-C14. None of the authentic residues contained palmitic or stearic acids. Three of the authentic glue residues – the creamware plate bottom and teapot lid and the Imari porcelain – showed the presence of abietic acid. The broken wig curler showed the presence of dehydroabietic acid. If pine resin were truly present in these samples from their original repairs, we would expect oxidation products to be present. Direct analysis of the soil from the cellar from which the authentic ceramics were excavated showed the presence of both abietic and dehydroxyabietic acids, indicating that the presence of these compounds in the glue residues are likely due to environmental contamination. The context soil also contained short even-chain fatty acids. The Mass Mountaineer (R. B. Cody, Peabody, MA) software provided for DART-MS data analysis provides a mechanism for comparing and matching spectra. Figure 4 shows a head-to-tail comparison between the 17th-c.glue from the punchbowl and the buried cheese glue. The search algorithm looks for significant similarities in both the ions present in the spectra and their intensities to make a match. The ions in the spectra that led to the buried cheese glue being considered a good match for the authentic glues do not correspond to any known compounds. This pattern was consistent across all of the authentic glue residues. We believe this is a consequence of similarities in burial context, and not related to similarities in the composition of the replica and authentic glues. A head-to-tail comparison of another of the authentic glue residues and soil from the Ferry Farm burial context is shown in Figure 5. Except for the ion at m/z 107.066, the strongest signals from the teapot lid glue residue correspond to those in the soil sample.



Figure 4. Head-to-tail comparison of authentic glue and replica cheese glue after 6 months of burial.

Figure 5. Head-to-tail comparison between DART mass spectra of soil (top) and buried replica cheese glue.



Conclusions Based on these results, we can draw two primary conclusions. DART-MS can differentiate between the replica glues without sample preparation, and a short hydrolysis step makes identification of collagenous glues possible without derivatization or chromatography. We were unable to identify the nature of the authentic glue residues on the ceramics excavated at Ferry Farm. This may be due to decomposition of the organic components of the glues, or contamination from the burial environment. The samples provided were too small to reliably weigh on the equipment available at EMU. As the bulk of these samples appears to have been carbonate, even good preservation of the organic content may not have provided detectable amounts of diagnostic compounds. Further studies are ongoing, with larger samples where more material was available for study. Quantitative analysis of the hydrolysates using both transmission DART and GC-MS will, we hope, shed further light on the nature of these unique residues.

Acknowledgments This work was supported by National Science Foundation MRI-R2 Award #0959621. Financial support was also provided by the Lourdes University Department of Chemistry and Physical Sciences, the EMU Provost’s Office (Faculty Research Fellowship for RAA) and the EMU Chemistry Department. Special thanks to Melanie Marquis and Silas Hurry for their contributions to the project.

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18th-Century Glue Recipes: Towards Identifying Glue Residues from

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