Raman microscopy and x-ray fluorescence analysis of pigments on medieval and Renaissance Italian manuscript cuttings

Italian medieval and Renaissance manuscript cuttings and miniatures from the Victoria and Albert Museum were analyzed by Raman microscopy to compile a database of pigments used in different periods and different Italian regions. The palette identified in most manuscripts and cuttings was found to include lead white, gypsum, azurite, lazurite, indigo, malachite, vermilion, red lead, lead tin yellow (I), goethite, carbon, and iron gall ink. A few of the miniatures, such as the historiated capital “M” painted by Gerolamo da Cremona and the Petrarca manuscript by Bartolomeo Sanvito, are of exceptional quality and were analyzed extensively; some contained unusual materials. The widespread usage of iron oxides such as goethite and hematite as minor components of mixtures with azurite is particularly notable. The use of a needle-shaped form of iron gall ink as a pigment rather than a writing material was established by both Raman microscopy and x-ray fluorescence spectroscopy for the Madonna and Child by Franco de’ Russi.

[1]  L. Burgio,et al.  RAMAN MICROSCOPY STUDY OF THE PIGMENTS ON THREE ILLUMINATED MEDIAEVAL LATIN MANUSCRIPTS , 1997 .

[2]  R. Clark,et al.  Identification of lead(ii) sulfide and pararealgar on a 13th century manuscript by Raman microscopy , 1997 .

[3]  R. J. Clark,et al.  The Lindisfarne Gospels and two other 8th century Anglo-Saxon/Insular manuscripts: pigment identification by Raman microscopy , 2004 .

[4]  Robin J. H. Clark,et al.  The role of H2S in pigment blackening , 2002 .

[5]  Dalva Lúcia Araújo de Faria,et al.  Raman microspectroscopy of some iron oxides and oxyhydroxides , 1997 .

[6]  Robin J. H. Clark,et al.  Raman microscopy in archaeological science , 2004 .

[7]  P. P. Lottici,et al.  Micro‐Raman investigation of iron oxide films and powders produced by sol–gel syntheses , 1999 .

[8]  Richard R. Hark,et al.  Spectroscopic investigation of modern pigments on purportedly medieval miniatures by the ‘Spanish Forger’ , 2009 .

[9]  Zdravko Rupnik,et al.  In-air PIXE set-up for automatic analysis of historical document inks , 2004 .

[10]  Peter A. Williams,et al.  Raman spectroscopic study of the basic copper sulphates-implications for copper corrosion and 'bronze disease' , 2003 .

[11]  B. Schrader,et al.  Near‐infrared fourier transform Raman spectroscopy of indigoids , 1995 .

[12]  R. L. Feller,et al.  Artists' Pigments: A Handbook of Their History and Characteristics, Volume 2 , 1995 .

[13]  Elizabeth Crumley,et al.  Artists' Pigments. A Handbook of Their History and Characteristics, Vol. 1 , 1989 .

[14]  Nancy K. Turner,et al.  Investigation of the painting materials and techniques of the late‐15th century manuscript illuminator Jean Bourdichon , 2009 .

[15]  C. Coupry,et al.  Raman Spectroscopic Investigation of Blue Contemporary Textiles , 1997 .

[16]  Paola Ricciardi,et al.  Nondestructive on‐site identification of ancient glasses: genuine artefacts, embellished pieces or forgeries? , 2009 .

[17]  L. Burgio,et al.  Pigment identification on medieval manuscripts, paintings and other artefacts by Raman microscopy: applications to the study of three German manuscripts , 1997 .

[18]  R. Clark,et al.  The resonance Raman spectrum of ultramarine blue , 1975 .

[19]  Robin J. H. Clark,et al.  Pigment identification by spectroscopic means: an arts/science interface , 2002 .

[20]  D. Thompson,,et al.  The materials and techniques of medieval painting , 1956 .

[21]  R. Clark,et al.  Peer Reviewed: Raman Microscopy of A 13th-Century Illuminated Text , 1998 .

[22]  K. Seddon,et al.  Non‐Destructive In Situ Identification of Cinnabar on Ancient Chinese Manuscripts , 1997 .

[23]  B. Kanngießer,et al.  Investigation of oxidation and migration processes of inorganic compounds in ink-corroded manuscripts , 2004 .

[24]  M. L. Curri,et al.  RAMAN MICROSCOPY : THE IDENTIFICATION OF LAPIS LAZULI ON MEDIEVAL POTTERY FRAGMENTS FROM THE SOUTH OF ITALY , 1997 .

[25]  P. Colomban.  Raman spectrometry, a unique tool to analyze and classify ancient ceramics and glasses , 2004, cond-mat/0701351.

[26]  Christopher De Hamel,et al.  A History of Illuminated Manuscripts , 1986 .

[27]  L. Burgio,et al.  Pigment identification studies in situ of Javanese, Thai, Korean, Chinese and Uighur manuscripts by Raman microscopy , 1999 .

[28]  L. Curri,et al.  Characterization of Brown–Black and Blue Pigments in Glazed Pottery Fragments from Castel Fiorentino (Foggia, Italy) by Raman Microscopy, X‐Ray Powder Diffractometry and X‐Ray Photoelectron Spectroscopy , 1997 .

[29]  A. Wattiaux,et al.  Mössbauer spectrometry applied to the study of laboratory samples made of iron gall ink , 2008 .

[30]  L. Burgio,et al.  Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[31]  Luc Moens,et al.  Micro-Raman spectroscopy of natural and synthetic indigo samples. , 2003, The Analyst.

[32]  K. Trentelman,et al.  Characterization of Pararealgar and Other Light-Induced Transformation Products from Realgar by Raman Microspectroscopy. , 1996, Analytical chemistry.

[33]  Dudley Creagh,et al.  Raman analysis of iron-gall inks on parchment , 2006 .

[34]  N. Eastaugh.  Pigment compendium : a dictionary and optical microscopy of historical pigments , 2008 .

[35]  M. Odlyha,et al.  Studies on the thermal decomposition of basic lead(II) carbonate by Fourier-transform Raman spectroscopy, X-ray diffraction and thermal analysis , 1996 .

[36]  Ivan P. Parkin,et al.  Atmospheric Pressure Chemical Vapor Deposition of Tin Sulfides (SnS, Sn2S3, and SnS2) on Glass , 1999 .

[37]  Ray L. Frost,et al.  Raman spectroscopic study of azurite and malachite at 298 and 77 K , 2002 .

[38]  Michael Doulgeridis,et al.  Pigment identification in paintings employing laser induced breakdown spectroscopy and Raman microscopy , 2001 .

[39]  Matija Strlič,et al.  Historical iron gall ink containing documents — Properties affecting their condition , 2006 .

[40]  L. Burgio,et al.  Raman spectroscopy as a means for the identification of plattnerite (PbO2), of lead pigments and of their degradation products. , 2001, The Analyst.

[41]  M. L. Curri,et al.  The identification by Raman microscopy and X-ray diffraction of iron-oxide pigments and of the red pigments found on Italian pottery fragments , 1998 .

[42]  Robert Withnall,et al.  Synthesis, Structural Characterization and Raman Spectroscopy of the Inorganic Pigments Lead Tin Yellow Types I and II and Lead Antimonate Yellow: Their Identification on Medieval Paintings and Manuscripts. , 1995 .

[43]  R. Clark.  Nyholm Lecture. Synthesis, structure, and spectroscopy of metal–metal dimers, linear chains, and dimer chains , 1990 .

[44]  R. Withnall,et al.  Identification by Raman microscopy and visible reflectance spectroscopy of pigments on an Icelandic manuscript , 1995 .

[45]  D. Fabbri,et al.  Effect of pigments on the analysis of fatty acids in siccative oils by pyrolysis methylation and silylation , 2005 .

[46]  Robert Withnall,et al.  Synthesis, structural characterisation and Raman spectroscopy of the inorganic pigments lead tin yellow types I and II and lead antimonate yellow: their identification on medieval paintings and manuscripts , 1995 .

[47]  C. Cooksey,et al.  Indigo, woad, and Tyrian Purple: important vat dyes from antiquity to the present , 1993 .

[48]  R. Hark,et al.  Spectroscopic Investigations of Bourdichon Miniatures: Masterpieces of Light and Color , 2009, Applied spectroscopy.

[49]  C. Cooksey,et al.  Monobromoindigos: a new general synthesis, the characterization of all four isomers and an investigation into the purple colour of 6,6′-dibromoindigo , 1999 .

[50]  Robin J. H. Clark,et al.  Raman spectroscopic library of natural and synthetic pigments (pre- ≈ 1850 AD) , 1997 .