Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis

Abstract One of the foremost challenges facing analysis of historical textiles is that the gold standard technique—high performance liquid chromatography (HPLC)—is inherently destructive. This is especially problematic considering many historical textiles are exceptionally fragile, be it from age, p...

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Main Authors: Caelin P. Celani, Ilaria Degano, Carolyn Chen, Olivia Jaeger, Amelia M. Speed, Karl S. Booksh, Jocelyn Alcantara-Garcia
Format: Article
Language:English
Published: SpringerOpen 2024-02-01
Series:Heritage Science
Subjects:
Online Access:https://doi.org/10.1186/s40494-023-01108-x
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author Caelin P. Celani
Ilaria Degano
Carolyn Chen
Olivia Jaeger
Amelia M. Speed
Karl S. Booksh
Jocelyn Alcantara-Garcia
author_facet Caelin P. Celani
Ilaria Degano
Carolyn Chen
Olivia Jaeger
Amelia M. Speed
Karl S. Booksh
Jocelyn Alcantara-Garcia
author_sort Caelin P. Celani
collection DOAJ
description Abstract One of the foremost challenges facing analysis of historical textiles is that the gold standard technique—high performance liquid chromatography (HPLC)—is inherently destructive. This is especially problematic considering many historical textiles are exceptionally fragile, be it from age, poor care over time, etc. One proposed solution to this is the implementation of non-destructive, namely spectroscopic, techniques, such as diffuse reflectance (Fiber Optic Reflectance Spectroscopy, FORS). In this work, 204 well-provenanced red Norwich textiles were measured with FORS and analyzed to attempt to determine chromophore combinations used to dye the original textiles. To these ends, cluster analysis algorithms and spectroscopic domain knowledge were coupled with selective HPLC validation to assess overall ability of FORS to discern changes in chromophore combinations. It was found that the near infrared (NIR) region of the spectrum contained little meaningful information in multivariate space, while the VIS region, particularly 380–469 nm, showed a narrow visible region that was primarily responsible for clustering behavior that correlates with HPLC-validated samples. This indicates that FORS shows promise for discerning chromophores in textile swatches. Additionally, X-ray fluorescence (XRF) analysis was used to confirm that the observed FORS spectral inflection point shift in the 600 nm region did not correlate with the presence or type of mordant used when dying these textiles. From this work, three main conclusions can be drawn: (1) FORS adequately identifies visual infon, which shows reasonable correlation to HPLC-validated dye recipes, warranting further investigation, and indicating utility for cois or use for those with visual impairments; (2) XRF analysis confirms that the ~ 600 nm inflection point shift and mordant are not correlated when measuring dyed textiles, unless mordant is present below analytical detection limits or not present at all; (3) many documented structural-to-spectral relationships established in the conservation literature are too weak in dyed textiles for statistical analysis and, by extension, expert spectral identification.
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spelling doaj.art-7405704794e3438d8ec2b08338482a1e2024-03-05T19:55:25ZengSpringerOpenHeritage Science2050-74452024-02-0112111810.1186/s40494-023-01108-xExploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysisCaelin P. Celani0Ilaria Degano1Carolyn Chen2Olivia Jaeger3Amelia M. Speed4Karl S. Booksh5Jocelyn Alcantara-Garcia6Department of Chemistry & Biochemistry, University of DelawareDipartimento di Chimica e Chimica Industriale, Università di PisaDepartment of Chemistry, University of North Carolina Chapel HillDepartment of Art Conservation, University of DelawareDepartment of Chemistry & Biochemistry, University of DelawareDepartment of Chemistry & Biochemistry, University of DelawareDepartment of Chemistry & Biochemistry, University of DelawareAbstract One of the foremost challenges facing analysis of historical textiles is that the gold standard technique—high performance liquid chromatography (HPLC)—is inherently destructive. This is especially problematic considering many historical textiles are exceptionally fragile, be it from age, poor care over time, etc. One proposed solution to this is the implementation of non-destructive, namely spectroscopic, techniques, such as diffuse reflectance (Fiber Optic Reflectance Spectroscopy, FORS). In this work, 204 well-provenanced red Norwich textiles were measured with FORS and analyzed to attempt to determine chromophore combinations used to dye the original textiles. To these ends, cluster analysis algorithms and spectroscopic domain knowledge were coupled with selective HPLC validation to assess overall ability of FORS to discern changes in chromophore combinations. It was found that the near infrared (NIR) region of the spectrum contained little meaningful information in multivariate space, while the VIS region, particularly 380–469 nm, showed a narrow visible region that was primarily responsible for clustering behavior that correlates with HPLC-validated samples. This indicates that FORS shows promise for discerning chromophores in textile swatches. Additionally, X-ray fluorescence (XRF) analysis was used to confirm that the observed FORS spectral inflection point shift in the 600 nm region did not correlate with the presence or type of mordant used when dying these textiles. From this work, three main conclusions can be drawn: (1) FORS adequately identifies visual infon, which shows reasonable correlation to HPLC-validated dye recipes, warranting further investigation, and indicating utility for cois or use for those with visual impairments; (2) XRF analysis confirms that the ~ 600 nm inflection point shift and mordant are not correlated when measuring dyed textiles, unless mordant is present below analytical detection limits or not present at all; (3) many documented structural-to-spectral relationships established in the conservation literature are too weak in dyed textiles for statistical analysis and, by extension, expert spectral identification.https://doi.org/10.1186/s40494-023-01108-xTextilesRedCochinealMadderNorwichChemometrics
spellingShingle Caelin P. Celani
Ilaria Degano
Carolyn Chen
Olivia Jaeger
Amelia M. Speed
Karl S. Booksh
Jocelyn Alcantara-Garcia
Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
Heritage Science
Textiles
Red
Cochineal
Madder
Norwich
Chemometrics
title Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
title_full Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
title_fullStr Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
title_full_unstemmed Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
title_short Exploring elucidation of red dye mixtures on woolen historical textiles via non-destructive spectroscopic analysis and multivariate cluster analysis
title_sort exploring elucidation of red dye mixtures on woolen historical textiles via non destructive spectroscopic analysis and multivariate cluster analysis
topic Textiles
Red
Cochineal
Madder
Norwich
Chemometrics
url https://doi.org/10.1186/s40494-023-01108-x
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