ABSTRACT—The X-ray fluorescence analysis of the pigments on eleven early American watercolors and sixteen fraktur, in three English and American paint boxes, and two fraktur painters' boxes, has established that both fraktur artists and their contemporary watercolorists used commercially available pigments. The availability of these pigments to both groups is noted not only by their actual use but also by historical evidence.

1 INTRODUCTION

THE PAPER CONSERVATION and Analytical Laboratories of the Winterthur Museum have participated in a joint project involving analysis of the pigments used in fraktur and early American watercolors.

The term fraktur properly describes a typeface popular in Germany from the sixteenth century and characterized by “fractured” letter forms. It now refers to the illuminated manuscripts of the Pennsylvania Germans, and other German settlers, made during the eighteenth and mid-nineteenth centuries as shown in Figure 1. In contrast is the second group, the watercolors, which are paintings by the rural early American people; see Figure 2.

Fig. 1. Fraktur “Taufschein of Johannes Kreniger” (61.1109), Courtesy of The Henry Francis du Pont Winterthur Museum

Fig. 2. Watercolor “View at Appoquinimink” (75.26), Courtesy of The Henry Francis du Pont Winterthur Museum

The objective of this study was to use X-ray fluorescence analysis to identify the chemical elements found in the pigments used by both fraktur artists and early watercolorists. It was hoped that through interpretation of this elemental data, pigments used by both groups could be identified; and that this information would either confirm or lay to rest the idea of the fraktur artist using products of the early American farm environs for his pigments. In addition, the analytical data might help in the authentication of a given painting, since the presence of certain pigments might permit more accurate dating.

2 HISTORICAL BACKGROUND

THE FIRST GROUP of Germans to arrive in Pennsylvania came in 1683, just two years after Charles II granted a charter for the land to William Penn. Some of them heard Penn speak on a missionary trip which he made to Germany in 1677; Penn, a zealous Quaker, saw Pennsylvania as a “Holy Experiment.” The Germans settled in what was aptly called Germantown, which remained the boundaries of their immigration until about 1710.

By 1717, the incoming Germans had begun to generate concern in the predominently Quaker and English city of Philadelphia. In 1727, an estimated 15,000 to 20,000 Germans were living in the colony.1 The height of the immigration was reached around 1750 with as many as twenty-two ships of Germans arriving a year.2 Between 5 and 10% of these Germans were “plain people” such as the Amish and Mennonites; the majority of the rest were “church people” such as the Lutheran and Reformed. Interestingly, this latter group produced most of the fraktur. At mid-century, the Germans formed about a third of Pennsylvania's population and had settled, for the most part, in the lands just west and northwest of Philadelphia.3

The contributions of the eighteenth century German settlers were rich and varied. They provided much of the trade in the prominent and rich city of Philadelphia. They introduced many modern agricultural methods. Their printers produced more books than those of New England and New York combined. Benjamin Franklin began a German newspaper for them in 1732, and also in Philadelphia, cabinetmakers printed their message in English and German on the same furniture label.

Education was important to the Germans. Communities are known to have built a schoolhouse before building a church. The penmanship sheets of writing specimens by the schoolmaster were teaching aids of the time. Awards of merit, too, were made by him. These manuscripts are fraktur. Other forms of fraktur include birth and baptismal certificates, house blessings and family records.

The first person to write about fraktur and bring it toward the fore was Henry Mercer, who, in 1897, said the following about a paint box used for fraktur:

“With great interest, we learned that the time-stained box found in one of the garrets of Bedminster had long ago in its longest compartment contained goose-quill pens, and brushes made of the hair of the domestic cat; that the caked colors in the small bottles had been the home-mixed inks and paints of the master once liquified in whiskey, and that the varnish was composed of the gum of the cherry tree diluted in water.”4

The implications from this, that fraktur were produced from farmyard products, have continued to the present day. Gilbert, in 1971, said, “Fortunately there were teachers trained in the art of fraktur who could instruct their pupils to write the alphabet and to illustrate the letters with homemade paints. Vegetable, plant, and berry dyes were probably used… .”5 Unfortunately glossed over by some was Mercer's comment in a catalog description in another presentation that, “the old paints were bought from apothecaries in Philadelphia and kept in bottles.”6

Among the scholars whose theories were that fraktur makers used known artist pigments is Frances Lichten. In a 1963 lecture on fraktur she said that she, as an artist, could easily recognize by eye the presence of such widely used pigments as vermilion, Prussian blue, gamboge and orpiment.7 Earlier, in 1937, Henry Borneman had stated:

…the colors appearing in these manuscripts are produced by inks and pigments. Column writers have suggested that their methods of producing colors were primitive and their results crude. An examination of hundreds of manuscripts had led me to the conclusion that these colorists were not mere experimenters in the making of inks and pigments. They used recipes which were handed down not only by tradition, but in many cases in manuscripts and in print.8

Borneman shares with us Johann Krauss's Haus und Kunst-Buch published in 1819 in Allentown, Pennsylvania. Krauss wrote of the use of carmine, annotto, Prussian blue, verdigris, and other colors. Also presented by Borneman is Ambrosius Henkel's Das Grosze ABC Buch, published in New Market, Virginia, which recommends Brazil wood, verdigris, and indigo.

Artists' colors were available to the countrymen through several sources. They came through local shops and peddlers, by special order from abroad (there was much correspondence to the homeland at that time) and from large cities. A newspaper advertisement, shown in Figure 3, in the Pennsylvania Journal, March 29, 1764, placed by James Peters, druggist and chemist in Lancaster, tells of items “Just imported in the last vessels at Philadelphia, from London… .” Included in the list are white lead, red lead, ocher, umber, Spanish brown, Prussian blue, verdigris, lamp black, ivory black, smalt, carmine, ultramarine, vermilion, flake white, and Indian ink.9 In the 1820's, domestic watercolors became available. These were first manufactured in America by the Osborne Company in Philadelphia.10

Fig. 3. Newspaper Advertisement, PENNSYLVANIA JOURNAL, March 29, 1764, Courtesy of The Historical Society of Pennsylvania

Also imported was paper. Since the beginning of the colonies, paper had arrived from abroad in a strong continous stream. The only major obstruction to this flow was from 1765 (the Stamp Act) through 1783 (the end of the American Revolution). After the war, paper resumed its course from Europe with such breadth that by the third decade of the nineteenth century its competition caused some drastic reductions in America's paper industry.11 That imported and domestic papers have been found used with fraktur is not surprising. Many early American paper-makers were Pennsylvania German, including the first, Wilhelm Rittenhouse, whose mill was erected near Germantown in 1690.

So we see that the Pennsylvania Germans' use of imported papers and paints is in harmony with their other, often progressive, contributions to their new world. As a foreign traveler in the eighteenth century noted: they must have been princes as their barns were so big!12

3 PIGMENT ANALYSIS

ELEMENTAL ANALYSIS by X-ray fluorescence was used in this study of painting materials. The technique, previously used in the determination of the chemical composition of silver, brass, pewter and glass,13, 14 was modified slightly for pigment analysis so that the 55Fe, 241Am, and 109Cd sources are successively employed to obtain data in three different adjacent portions of the 0–40 keV spectrum. Potassium, calcium, titanium, and vanadium are detected by a 100 second irradiation on the 55Fe source; silver, tin, antimony, barium and others with a 100 second irradiation on the 241Am source, and copper, iron, zinc, lead, arsenic, mercury, chromium, and others of particular interest with regard to pigment analysis with a 300 second irradiation on the 109Cd source. Whatman No. 541 filter paper is used to obtain a baseline; x-ray fluorescence data from this paper are subtracted by the computer from the pigment data line. In addition, a clear unpigmented portion of the painting is analyzed when possible. In this way, any elements which may be in the paper can be manually subtracted out. Peak locations are determined by using a reference glass standard which contains thirty different elements. Count data and graphical plot of each pigmented area are obtained, then interpreted.

While pigment samples could have been removed from the fraktur and watercolors being studied, we chose not to do so. Rather, our efforts were directed toward demonstrating the utility for pigment analysis of a technique already available in our laboratory. Without the removal of any sample, even the most minute, x-ray fluorescence analysis, although not providing a complete description of the pigment, frequently provided sufficient information on elemental composition to permit reliable conclusions as to the identity of pigments. Further, the rapidity of the technique permitted the analysis of more than 100 pigmented areas in only a few days time.

X-ray fluorescence analysis does have certain limitations. Since the technique is not sensitive to elements below atomic number 19, pigments which are metal acetates, silicates, aluminates, etc. cannot be fully characterized. Similarly, organic dyes are not detected except by the absence of metal cations. If the pigmented area is small, the elements present in neighboring areas may obscure those in the area of interest. Finally, analytical data obtained on colors made of two or more pigments, e.g. Prussian blue mixed with an organic yellow to form green, may be subject to misinterpretation.

The first step in attempting to resolve the controversy surrounding the source of fraktur painters' materials was to examine the pigments used by watercolor painters in the period 1750–1850. To this end, the pigments in three watercolor paint boxes in the Winterthur collection, and those of a group of non-fraktur American watercolors from the same time period were analyzed.

Although the first box, of English origin, is itself authentic, dating from the late eighteenth century, analysis of the pigments showed that several of them were not available until sometime later. A yellow pigment, for example, contained both lead and chromium indicating it was chrome yellow (PbCrO4), a pigment which did not become available on a commercial scale until 1818. A second paint box (England, early nineteenth century) contained about forty watercolor cakes, rather than powdered pigments. The elemental compositions of these cakes are summarized in Table I. In a few instances in this Table as well as Table II, elements expected on the basis of the label identification are absent; in other cases, additional unexpected elements are present. More study on these is desirable but was not undertaken as part of this project. For the most part, the elements found in the pigment cakes and the pigment identifications based upon them are consistent with their attributed dates.

TABLE I ELEMENTS FOUND—PAINT BOX (68.1828) REEVES & INWOOD—ENGLISH, 19TH CENTURY

TABLE II ELEMENTS FOUND—PAINT BOX (65.1303) G. C. OSBORNE, PHILADELPHIA—AMERICAN C.1826

The third paint box examined was made by Osborne and Company of Philadelphia in 1826. Although the pigment cakes are fewer in number than in the second English paint box, one should not assume that American watercolorists had a limited selection of pigments available to them.

Note among the pigments in the Osborne box (Table II) the presence of vermilion, Prussian blue, chrome yellow, several iron containing umbers and siennas, and others.

Data from the analysis of the pigments of eleven non-fraktur watercolors, summarized in Table III and discussed below suggests, however, that even though large numbers of pigments were available, only a few were actually used to any extent.

TABLE III PIGMENTS INDICATED ON ELEVEN WATERCOLORS AMERICAN, C.1700–1850

1. Red. All eleven watercolors had red areas, eight of which contained appreciable amounts of mercury. The presence of mercury indicates that the pigment used was vermilion, a red mercuric sulfide, a pigment in use since classical times, and manufactured in Europe since the early medieval period. An iron oxide red—probably red ocher, another ancient pigment—appeared in two of the eleven watercolors. A third red pigment, which visually appeared quite different from the others, was thought to be organic, probably a lake, since no x-ray fluorescence peaks attributed to red inorganic pigments were found.
2. Blue. Prussian blue (iron ferricyanide), well known as a pigment in Europe by 1750, was used on six of the eight watercolors with blue areas. Azurite or blue verditer, a basic copper carbonate, appeared on one.
3. Green. Verdigris, a basic copper acetate, and green earth, an iron-containing hydrosilicate, are equally represented among the watercolors tested—four each. Scheele's green or possibly Paris green, both characterized by the presence of copper and arsenic, appears on one watercolor.
4. Yellow. A wider variety of yellow pigments was found. Chrome yellow, or lead chromate, not commercially available until 1818, appears on a watercolor with an attributed date of 1810–1825. The presence of chrome yellow places this watercolor at or near the very end of that period. An organic material, possibly gamboge or another yellow pigment, appears on two paintings, and orpiment on one. Yellow ocher, present on three paintings, seems to have been the yellow pigment used with greatest frequency.
5. Brown and Black. The brown areas on half of the brown and black group were either iron containing pigments or iron gall ink. Differentiation between the various iron ochers, sienna, and inks is not possible by x-ray fluorescence. In one case, the iron was accompanied by arsenic, suggesting the use of an obscure pigment called terra di Siena which is not listed by the usual reference sources.15, 16 A similar pigment containing both iron and arsenic was found among the English pigment cakes. Bone black, indicated by the presence of a large calcium peak and the absence of any other peaks, was found on two of the paintings and carbon black on one.
6. White. A distinctive feature of many of the watercolors was the ubiquitous presence of lead. Seven of the eleven watercolors contained lead—in white areas, in paler hues, and as an opacifier in the effort to achieve an effect more similar to that of oil painting.

How do the pigments of fraktur compare with those found on early American watercolors? The findings on sixteen fraktur are summarized in Table IV and discussed below.

TABLE IV PIGMENTS INDICATED ON SIXTEEN FRAKTUR AMERICAN, C.1780–1850

1. Red. Fifteen fraktur had red pigmented areas which contained mercury, indicating the use of vermilion. The other red pigment found was red ocher. Both of these pigments were found on the non-fraktur watercolors.
2. Blue. Prussian blue, the blue pigment of choice of watercolorists, was also widely used on the fraktur tested, appearing on nine. Smalt, which appears on one fraktur, is indicated by the presence of both cobalt and arsenic.
3. Green. A copper green, in most cases probably verdigris, a basic copper acetate appears on ten fraktur. The fact that many of the green areas have turned quite brown indicates the use of verdigris rather than copper resinate in those areas, since verdigris readily decomposes in the presence of water and heat to form a dark residue, cupric oxide, while copper resinate remains somewhat protected by the resinous medium. Verdigris and the other green pigment occasionally used, green earth, have both been known and in use since antiquity.
4. Yellow. Of the fifteen fraktur with yellow areas, the majority, ten, appeared to contain an organic material as a colorant. The supposition is that gamboge, an organic resin in wide use at the time, was the pigment used. Other possibilities include Indian yellow, annotto and saffron. Since x-ray fluorescence is not sensitive to organic materials, the pigment's exact identity is not known. Yellow ocher, another iron oxide, and orpiment, both widely used since classical times, are also represented. Of greatest interest is the presence of chrome yellow or lead chromate in three of the fraktur. All three fraktur which bear this pigment postdate the commercial appearance of chrome yellow in 1818, but not by much. This evidence strongly suggests that fraktur painters had ready access to new pigments soon after their introduction.
5. Brown and Black. Since fraktur are frequently pen and ink drawings painted in with other colors, many of the brown and black areas are of the same iron gall ink used to outline the figures. A homemade iron gall ink was in common use by all members of society, not just Pennsylvania Germans. Other black and brown areas which differ in appearance from the ink areas and also iron-containing pigments are not differentiable by x-ray fluorescence from the iron inks.
6. White. Lead white seems to have been used sparingly by fraktur artists. A lead-containing pigment was occasionally found mixed with a red pigment, probably vermilion, to make a pink color, or mixed with vermilion or Prussian blue to achieve an opaque effect. However, the presence of large quantities of lead white in all parts of a watercolor seems to be a technique used primarily by non-fraktur watercolorists. The fraktur artists were calligraphers who decorated their often functional documents with ornamental drawings, whereas for the non-fraktur watercolor artists, the emphasis lay in painterly techniques.

For further information on the pigments used, we turned to two fraktur painters boxes in the collection of the Mercer Museum17; see Figure 4. A blue material from one bottle was Prussian blue. Among the pigments found in the second box (Table V) were white lead, two samples of Prussian blue, chrome yellow, vermilion, and terra di Siena. The last color was previously found in one watercolor and the wooden English paint box. Its presence in one of these fraktur painter's boxes is particularly significant since it ties together both fraktur and non-fraktur watercolor paintings with a known commercially available but perhaps little used pigment.

Fig. 4. Fraktur Painter's Box (No. 25370), Courtesy of the Mercer Museum of the Bucks County Historical Society

TABLE V PIGMENTS FROM FRAKTUR PAINTER'S BOX MERCER MUSEUM NO. 25370

These data from the analysis of pigments on sixteen fraktur, together with those from the fraktur painters' bottles, refutes the idea that fraktur pigments came only from local farmlands and gardens. The confusion seems to have arisen from Henry Mercer's statement that the artist's paint bottles contained “home-mixed inks and paints”. Home-mixed—yes. The commercially bought powder or cake pigments were undoubtedly mixed with a medium or binder. These pigments were not, however, home-made, that is extracted from local plants and berries.

4 CONCLUSION

IN SUMMARY, the x-ray fluorescence analysis of the pigments on eleven early American watercolors, sixteen fraktur, in three English and American paint boxes, and two fraktur painters boxes has shown that both fraktur artists and their contemporary watercolorists, used commercially available pigments. The availability of these pigments also is noted by the historical evidence. Newspapers, furniture labels, advertisements and trade cards as shown in Figure 5 attest to the availability of a wide variety of commercial products from the trade centers of Philadelphia and Lancaster. Not the least among these were artistsa' painting materials. As a card by the Osborne Company, pigment makers of Philadelphia, states “Booksellers, Druggists and Country Storekeepers all supplied on liberal terms”.18

Fig. 5. Trade Card (66 � 93.4) Osborne and Company, Philadelphia, c.1843, Courtesy of The Henry Francis du Pont Winterthur Museum, Joseph Downs Manuscript Collection

REFERENCES

Joseph E.Illick, Colonial Pennsylvania: A History, (New York: Charles Scribner's Sons, 1976), p. 123.

Russell WeidnerGilbert, A Picture of the Pennsylvania Germans, Pennsylvania History Studies: No. 1, (Gettysburg: The Pennsylvania Historical Association, 1971), 3rd edition, pp. 6–7.

Gilbert, Pennsylvania Germans, p. 11–12.

HenryMercer, “The Survival of the Medieval Art of Illuminative Writing Amoung Pennsylvania Germans”, (Proceedings of the American Philosophical Society, 36, no. 156 (1897), p. 424.), reprinted in Contributions to American History, No. 2, (Doylestown, Pa.: The Bucks County Historical Society).

Gilbert, Pennsylvania Germans, p. 49.

Henry C.Mercer, Tools of the Nationmaker, (Doylestown, Pa: Bucks County Intelligencer, 1897), p. 65.

FrancesLichten, The Illuminated Manuscripts of the Pennsylvania Dutch, (Philadelphia: Free Library of Philadelphia, 1958), p. 24.

HenryBorneman, “Pennsylvania German Illuminated Manuscripts”, Proceedings of the Pennsylvania German Society, 46, (1937), p. 41.

Monroe H.Fabian, Associate Curator, National Portrait Gallery, Washington, D.C., personal letter.

Lichten, Illuminated Manuscripts, p. 24.

John W.Maxon, Jr., “American Papermakers in the Great Tariff Debate”, The Paper Maker, 31, no. 1 (1962), pp. 23–24. In 1820, the petition “The Memorial of the Society of Paper Makers of the States of Pennsylvania and Delaware” was presented to Congress. It reflected the times: The district we represent offers, we think, a comparative view of the state of this manufacture in the country at large—In this seventy Paper Mills, are erected which were in full operation, until the imporations after the late war; in these there were ninety-five paper vats…employing nine hundred and fifty persons…; and from the causes we have mentioned we find that there remain but seventeen vats at work… leaving unemployed 775 persons….

JosephKindigIII, introductory lecture to “The Pennsylvania German Influence on American Decorative Arts”, Pennsbury Manor Americana Forum, Pennsbury, Pennsylvania, September, 1977.

V. F.Hanson, “Quantitative Elemental Analysis of Art Objects by Energy Dispersive X-ray Fluorescence Spectroscopy”, Applied Spectroscopy, 27, no. 5 (1973), pp. 309–334.

J. H.Carlson, “X-ray Fluorescence Analysis of Pewter: English and Scottish Measures”, Archaeometry, 19, no. 2, (1977), pp. 147–155.

J. R.Gettens and G. L.Stout, Painting Materials, A Short Encyclopedia, (New York: Dover, 1966).

R. D.Harley, Artists' Pigments, c.1600–1835, (New York: American Elsevier, 1970).

Grateful acknowledgement is made to the Mercer Museum, Doylestown, Pa., for the lending of the pigments for analysis.

Trade Card (66 � 93.4), Osborne and Company, Philadelphia, c. 1843, The Joseph Downs Manuscript and Microfilm Collection, Winterthur Museum, Winterthur, Delaware.

Section Index