Synthetic arsenic sulfides in Japanese prints of the Meiji period
© The Author(s) 2016
Received: 10 February 2016
Accepted: 10 May 2016
Published: 5 July 2016
A multi-analytical investigation of Japanese woodblock prints ranging in date from 1864 to 1895 and covering essentially the time span between the very end of the Edo period and the middle of the Meiji period showed a widespread use of arsenic sulfides for yellow and green colored areas (the latter obtained by mixing Prussian blue to the yellow arsenic sulfides). Analysis by optical microscopy, X-ray fluorescence spectroscopy, Raman microscopy, and Scanning Electron Microscopy confirmed that the yellow pigment is usually a compound belonging to the solid solution series (As8S8)–(As8S9). The poor crystallinity of the pigment as shown by Raman microscopy, the non-stoichiometric As/S ratio, as well as the presence of excess uncombined sulfur point to a synthetic origin for the pigment. Period literary sources suggest that synthetic arsenic sulfide pigments manufacture might have started in the Iwashiro province in 1846. This is to our knowledge the first conclusive evidence for the use of synthetic arsenic sulfides in woodblock prints in Japan.
Because of their vivid colors, ranging from yellow to red, arsenic sulfides were used as pigments since ancient times [1, 2]. Natural arsenic sulfide pigments differ for their As:S ratios, and include realgar (α-AsS), pararealgar (β-AsS), and orpiment (As2S3). Realgar, a widely used orange/red pigment, occurs in low-temperature hydrothermal deposits [3–5]. Pararealgar is the light-induced degradation yellow form of realgar and alacranite [6, 7]. Mixtures of pararealgar and/or realgar have been systematically observed in many studies [8–10]. Orpiment was widely used as a yellow colorant besides yellow ochre since ancient times . Another arsenic sulfide, alacranite (As8S9)  is a rather uncommon red mineral showing a complicated crystallographic structure where clusters of As4S4 (realgar-type) and As4S5 coexist in an ordered cagelike structure . Although rare in nature, alacranite has been documented in works of art as a possible artificial product deriving from the arsenolite smelting [13–15]. The production of artificial orpiment in Western Europe was first mentioned by Johannes Alcherius in his recipe collection (1380–1420) , but the very first description of this synthetic pigment was made by Cennino Cennini in his treatise . According to these and later sources artificial orpiment was initially obtained by sublimation, using the dry-process method . The wet-process method, which produces a yellow precipitate, was introduced at the end of the nineteenth century [2 and references therein, 18].
Characterizing arsenic sulfide pigments and accurately distinguishing between natural and synthetic origin is a challenging chemical and crystallographic problem which requires a multi-analytical approach. Techniques such as polarized light microscopy (PLM), micro-Raman spectroscopy (RM), X-Ray Fluorescence spectrometry, X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive microanalysis (SEM-EDS)  are best suited to this task: some of them allow non-invasive analysis while others require microsampling. An in-depth study carried out on natural and artificial orpiment, the latter obtained through both wet- and dry-process, pointed out how only the results from the combination of several techniques allowed to identify the actual nature of the pigment [2, 14]. In particular, the presence of spherules of arsenic sulfide glass or alacranite solid solution series (As8S8)–(As8S9) was shown to be conclusive evidence for an artificial origin for orpiment .
List of the prints analyzed in this research, complete of dates, authors, and titles
No. 35, Nakanuma Chûbei attacks Michihide in the Dark of Night (Nakanuma Chûbei an’ya ni Michihide o tsuku), from the series “Fifty-four Scenes from the Story of Hideyoshi” (Hisago gundan gojûyojô)
The actor Kawarazaki Gonjûrô, from the series “Shindô Suikoden
Death memorial portrait (shini-e) of the actor Kawarazaki Kunitarô, d. 1867-04-21, age 19
Daimon Gate at Shiba Zôjôji Temple, from the series Famous Views of Tokyo (Tôkyô meishô zue)
The Cleaning-up Job (Ato kara gakari), from the series, Thirty-two Fashionable Physiognomies (Tôsei sanjûnisô)
Nakamura Chûzô as Konkara-bô and Sawamura Tosshô as Seikô-bô in the kabuki play “Oni mo jûshichi.” Possibly one panel of triptych
Kuruma-ôgi restaurant, Shinmei-mae, with geisha Matsutoku of Shinmei, from the series “Tôkyô sanjûroku kaiseki” (Thirty-six famous restaurants in Tokyo)
The three brothers in the kabuki play Sugawara denju tenarai kagami” (Sugawara and the Secrets of Calligraphy): Arashi Rikan as Sakura-maru, Nakamura Fukusuke as Umeo-maru, and Ōtani Tomoemon as Matsu-o-maru. Chûban triptych, Osaka
Ikenohata Shinobazu Benten, from the series “Tôkyô meisho sanjûroku gesen” (Thirty-six Comic Views of Tokyo)
Hamamatsu, from the series “Shoga gojûsan eki” (Calligraphy and Pictures for the Fifty-three Stations of the Tôkaidô)
Kawarazaki Gonnosuke as Nanbei (actually Abe no Munetô) in Adachigahara in Ōshû (Ōshû Adachigahara). Center panel of triptych
Bandô Hikosaburô as Yakko in the kabuki play Kotobuki Utsubozaru. Right sheet of triptych
Police raid on unlicensed prostitutes, illustration of news story from No. 425 of Yûbin Hôchi Shinbun
Nos 5-8, in series Lineage of the emperors of Japan (Honchô Kôtôki)
News from Kagoshima (Kagoshima Nippô)
The Two Generals Face off at the Battle of Kawanakajima in Shinshû (Shinshû Kawanakajima ryôshô jikisen no zu)
Shinagawa-machi Manrin Restaurant from the series Thirty-six Restaurants of Enlightenment (Kaika sanjûroku kaiseki)
Nakamura Sôjûrô as Chichibu Shigetô in kabuki play “Nichô no yumichigusa no Shigetô.” Center panel of a triptych
Kyôbashi Brick Buildings (Kyôbashi rengaishi), from the series Beauties in the Famous Places of Tokyo (Tôkyô meisho bijin awase)
The courtesan Ô-Yodo of Kinkanrô, from the series A Ranking of the Pleasure Quarters (Hana no kuruwa zensei kurabe)
Lively Poetry Gathering (Uta-awase no nigiwai), with Meiji empress in the center
Panorama of the Precincts of Sensôji Temple in Asakusa (Asakusa-ku Kinryûzan Sensôji keidai ichiran), from the series Famous Places of Tokyo (Tôkyô meisho no uchi)
Enjoying a comparison of the flowers of the four seasons
Shin-Yoshiwara Hachimanrô, from the series Embellishments for Thirty-Six Flowers (Junshoku sanjûroku kasen)
Onoe Taganojô as Takao, from the kabuki play Mukashi hinagata date no utsushi-e. Right sheet of a triptych
Counting Song for Enlightened Education (Kaika kyôiku kazoeuta)
Ichikawa Danjûrô as Katô Toranosuke (L) and Hashiba Hisayoshi (C), and Ichikawa Sadanji as Hihôden (R), in the kabuki play Hanamidoki Hisago Taikôki
Cherry Blossoms at Asakusa Kannon Temple (Asakusa Kanzeon no sakura)
From the Eighteen Great Kabuki Plays: Kanjinchô (Kabuki jûhachiban no uchi: Kanjincho). Nakamura Fukusuke as Minamoto Yoshitsune, Ichikawa Danjûrô as Musashibô Benkei, and Ichikawa Sadanji as Togashi Saemon
Women’s Ceremonies: Poem Contests (Onna reishiki uta-awase)
Index sheets for the series The Inner Palace of Chiyoda (Chiyoda no Ôoku)
For woodblock prints, a commercial form of art, the use of cheaper pigments is generally expected, making the use of natural orpiment, usually an expensive pigment, quite unlikely. In her study, Yamato used the appearance of the pigment under optical microscopy observation to distinguish between synthetic and natural arsenic sulfides. In this study, we offer a fully multianalytical classification based on optical microscopy, Raman microscopy, and Scanning Electron microscopy with Energy Dispersive Spectrometry.
30 Japanese prints dated from 1864 to 1887 were selected for the analyses. A complete list of the prints alongside with their titles and authors is reported in Table 1.
A multi-technique approach, which includes micro-X-ray fluorescence, micro-Raman spectroscopy and Scanning Electron Microscopy equipped with Energy Dispersive Spectrometry, was followed in this study. The use of X-ray Diffraction was ruled out because of the small dimensions of the pigment particles and the low pigment coverage, which would have resulted in unacceptably large samples.
Micro X-ray fluorescence (micro-XRF) measurements were acquired with a Bruker ARTAX 400 instrument using unfiltered Rh radiation at 50 kV, 700 μA. Spectra were acquired with a 1 mm collimator for 120 s live-time accumulations.
Micro-Raman spectra were acquired with using a Bruker Senterra™ dispersive Raman microscope system, operating at 785 nm. Raman spectra were acquired directly from the prints using an Olympus LMPlanFL 50× long working distance objective, at a spectral resolution of 3–5 cm−1 and 30 s integration time. To avoid degradation or heat induced physical changes, the power at the laser injection port was limited to 1 mW. Integration times of 30 s were employed and three accumulations were averaged for each spectrum to obtain an adequate signal-to-noise ratio. Spectra were acquired and processed using the Opus 7.0 Raman software.
Pigment coated paper fiber samples for SEM-EDS analysis were mounted on aluminum stubs using a carbon adhesive tab and coated with a 10 nm carbon layer. SEM analyses (backscattered electron images and point analyses) were performed with a FE-SEM Zeiss Σigma HD, equipped with an Oxford Instrument X-MaxN 80 SDD detector. EDS microanalyses were run at 20 kV acceleration voltage and a working distance of 8.5 mm. Data were acquired and processed using the AZtec software system, v. 2.2 SP2 (Oxford Instruments).
Results and discussion
The majority of data was initially acquired by using non-destructive techniques, and for all the prints the same analytical approach was followed: XRF was systematically run on all the colored portions of each print, then, according to the elemental composition Raman measurements were acquired on selected areas. Finally, selective sampling was carried out to proceed with SEM-EDS analyses.
XRF data for green and yellow areas show the presence of arsenic and sulfur with other minor elements, notably iron, due to the paper matrix. The iron concentration seems higher in the green areas, possibly reflecting the use of Prussian blue mixed with the yellow to obtain the green shade.
The strong characteristic peaks at 329 and 340 cm−1 may be attributed to the monomer units in the alacranite structure, forming the shoulder at 360 cm−1. The insert in Fig. 1 shows also the characteristic peaks at about 349 and 355 cm−1, which may be assigned to the deformation and cage breath of the monomer As4S4 .
In all the prints from late Edo to Meiji period analyzed in this study, the systematic presence of arsenic and sulfur for the yellow and green colors indicates the use of arsenic sulfide-based pigments. This is consistent with results obtained by Yamato .
Micro-Raman spectroscopy showed the presence of alacranite and sulfur in the yellows, with additional Prussian blue added to obtain the green shades. The mixture of arsenic sulfide and Prussian blue explain the higher iron concentration detected by XRF in the green pigments. The broadening of the alacranite bands in the range between 329 and 340 cm−1, indicative of the presence of amorphous arsenic sulfide glass is consistent with the use of synthetic arsenic sulfides as shown by Vermeulen et al. . Likewise, the presence of free sulfur has been interpreted by Vermeulen et al.  as due to the dry-process method used to synthesize the pigment. SEM-EDS analyses further strengthen this hypothesis, since the presence of alacranite spherules (Fig. 3b), with non-stoichiometric ratio between arsenic and sulfur, is indicated in literature as the evidence for synthetic arsenic sulfides produced by dry-process rather than a wet-process method [2, 14, 15]. Interestingly, the analyses of the Aizu synthetic arsenic sulfide pigment carried out by Takamatsu in 1878 also show excess free sulfur .
The production of arsenic sulfides by sublimation from burning arsenolite and sulfur, dates back to the fourteenth century in Western Europe, but no sources have been found about their production in East Asia. The only reference known, that of Takamatsu in 1878 , refers to a possible production of artificial orpiment in Japan in about 1846, by burning arsenical stones with sulfur, in Aizu (in the present Fukushima prefecture). The very low concentration of copper may be explained by the exploitation of arsenic ores related to copper mining, largely attested in Japan [26–28].
The evidence presented in this study demonstrates that synthetic arsenic sulfide pigments were most likely manufactured in Japan in the late Edo period and in the early Meiji period. We show conclusively that this pigment was commonly used in woodblock printing, probably due to its low cost and easy availability. Takamatsu  reports “large scale” manufacture of orpiment in the Aizu region in northern Japan, and mentions the use of the pigment for tinting varnishes and painting book covers. No mention is made however of its use for woodblock prints. Takamatsu reports also that manufacture of synthetic orpiment would have started after 1846: while it is tempting to correlate this report with the finding of realgar (likely available and mined in the prefecture of Gunma) in several Edo period prints in the collection of the Metropolitan Museum of Art (results unpublished), a full study of arsenic pigments in Edo period woodblock prints will need to be carried before giving excessive weight to this date.
Finally, Takamatsu’s article also allows us to compare the price of artificial orpiment with that of gamboge, an imported and expensive yellow pigment also traditionally used on woodblock prints. The price of synthetic orpiment is quoted as 42 sen per 1 kin, while that of gamboge is 1.35 yen per 1 kin. At 100 sen to the yen, synthetic orpiment is less than one third the price of gamboge, making it a very attractive pigment for the woodblock printing trade.
The prints selected for analyses were assembled and dated by HDS, II. XRF and Raman data was collected by YL. SEM–EDS analyses were carried out by EB. The manuscript was prepared by YL, EB, and ML. All authors read and approved the final manuscript.
YL gratefully acknowledges the support of the Advanced Interdisciplinary Innovation Research Project of Sichuan University (skqy201216).
The authors declare that they have no competing interests.
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