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Towards the identification of dyestuffs in Early Iron Age Scandinavian peat bog textiles

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A large systematic dye investigation of prehistoric Danish and Norwegian bog textiles was carried out using high performance liquid chromatography with photo diode array detection. After the selection of the most suitable protocol for dye extraction and HPLC analysis for this specific group of archaeological samples, the second part included the characterisation of the dyes detected in the whole series of the Early Iron Age textiles and the interpretation of the dyeing technology. Natural organic dyes were found from the three main categories of natural dyes, hence throwing new light on the use of biological dye sources in Early Iron Age Scandinavia. The results clearly indicate that most Scandinavian peat bog textiles originally were dyed and that already during the 1st millennium BC, the populations in Scandinavia were familiar with dyeing technology.
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Towards the identification of dyestuffs in Early Iron Age Scandinavian
peat bog textiles
I. Vanden Berghe
a
,
*
, Margarita Gleba
b
, Ulla Mannering
b
a
Royal Institute for Cultural Heritage (KIK/IRPA), Jubelpark 1, B-1000 Brussels, Belgium
b
The Danish National Research Foundation’s Centre for Textile Research, University of Copenhagen, 102 Njalsgade, 2300 Copenhagen S, Denmark
article info
Article history:
Received 7 November 2008
Received in revised form
8 April 2009
Accepted 26 April 2009
Keywords:
Natural organic dyes
Dye extraction
High performance liquid chromatography
Archaeological textiles
Scandinavia
Early Iron Age
abstract
A large systematic dye investigation of prehistoric Danish and Norwegian bog textiles was carried out
using high performance liquid chromatography with photo diode array detection. After the selection of
the most suitable protocol for dye extraction and HPLC analysis for this specific group of archaeological
samples, the second part included the characterisation of the dyes detected in the whole series of the
Early Iron Age textiles and the interpretation of the dyeing technology. Natural organic dyes were found
from the three main categories of natural dyes, hence throwing new light on the use of biological dye
sources in Early Iron Age Scandinavia. The results clearly indicate that most Scandinavian peat bog
textiles originally were dyed and that already during the 1st millennium BC, the populations in Scan-
dinavia were familiar with the dyeing technology.
Ó2009 Elsevier Ltd. All rights reserved.
1. Introduction
Ancient textiles are rare finds in archaeology but, in Scandinavia,
wet, acidic, low oxygen or completely anoxic conditions and the
presence of polysaccharide sphagnan in the peat bogs (Painter,
1995, 1998; van der Sanden, 1996, 18) have preserved a large
number of prehistoric textiles (Hald, 1980; Mannering and Gleba,
forthcoming). Most of these finds date to the Scandinavian Early
Iron Age (500 BC–AD 400), when the custom of depositing objects
in the bogs was practiced by the prehistoric inhabitants of this
region. The majority of textiles have been found in Denmark (Hald,
1980). Two finds are known from Norway (Halvorsen, forthcoming)
and one from Sweden (Franze
´n et al., forthcoming). Most objects
were found in the 19th and the first half of the 20th century, when
peat was excavated as heating material.
The bog textiles constitute one of the largest and best-preserved
collections of prehistoric textiles in existence. In 2006, the Danish
National Research Foundation’s Centre for Textile Research initi-
ated the research program ‘Textile and Costume from Bronze and
Early Iron Ages in Danish Collections’ in order to examine the entire
corpus of Danish bog textiles. The study of Danish bog finds
warranted a closer look at the question of DYEING in Early Iron Age
Scandinavia.
A wide variety of plant and animal sources are known as
potential sources for the production of textile dyes (Cardon, 2007).
The most practical way to classify the natural organic dyes is on the
basis of the methods of their application. In this respect, three main
categories are to be distinguished as the direct, the vat and the
mordant dyes. Direct dyes are water-soluble and have affinity for
fibres in the dye bath. Within this group, well-known dyes are orchil
and saffron. Vat dyes are not soluble in water. Prior to the dyeing,
they are reduced into the water-soluble leuco-form to impregnate
the textile. Once in the fibre, they are brought back totheir insoluble
form by oxidation. Indigo, woad and Tyrian purple belong to this
group. Most natural organic dyes however are mordant dyes.
Although they are soluble in water, they have no affinity for the fibre.
A mordant, which can be either a tannin or a soluble metal salt, is
required for the binding of the dye to the fibre. The type of mordant
applied will determine the final colour of the dyed fabric. Thus,
madder dyed in the presence of alum will produce a bright red
colour, while a violet shade will be obtained by using iron.
While several studies of organic dyes found in Scandinavian
archaeological textiles have been reported during the 1980s
(Bender Jorgensen and Walton, 1986; Walton, 1986, 1988), until
now it was considered that the earliest dyed fabrics in Scandinavia
were the blanket from the Danish bog at Skærsø (Østergaard, 1994),
dated to the 1st century BC and textile fragments from the Danish
burial at Lønne Hede, dated to the 1st century AD (Walton, 1986).
Furthermore, Scandinavian dyeing technology has been largely
*Corresponding author. Tel.: þ32 2 739 6846; fax: þ32 2 732 0105.
E-mail address: ina.vandenberghe@kikirpa.be (I. Vanden Berghe).
Contents lists available at ScienceDirect
Journal of Archaeological Science
journal homepage: http://www.elsevier.com/locate/jas
0305-4403/$ see front matter Ó2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2009.04.019
Journal of Archaeological Science 36 (2009) 1910–1921
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connected to Roman influences in Northern Europe and the
majority of extant analyses have been performed on the finds dated
to the Roman Iron Age (AD 1–400) (Walton Rogers, 1995).
The first part of the study was dedicated to the selection of the
most suitable protocol for dye extraction and HPLC analysis for this
specific group of archaeological samples. Several different recently
published soft extraction methods and methods showing improved
sensitivity were evaluated, first on references, later on a limited set
of archaeological samples. One of these methods was chosen for the
analysis of the complete series of the Early Iron Age textiles.
2. Materials and methods
2.1. Sources of samples and their description
Due to the long sojourn in the tannin-rich peat bog environ-
ment, the present colours of the textiles vary from light brown to
reddish brown to almost black. Although several textiles actually
still have reddish and greenish shades suggesting the use of dyeing,
it is no longer possible to identify the original colour visually or
under the microscope. In some cases the colours are even
misleading: thus, in the Bredmose scarf (sample 181), the reddish
yarn, creating a grid check pattern tested positive for indigotin.
Only in the case of one find, the band from Huldremose I (sample
144), the present greenish brown colour suggested the original
presence of blue dye. Furthermore, the majority of these fabrics are
patterned with checks or stripes, achieved by using different
naturally pigmented wools. Therefore, in this study both warp and
weft yarns were sampled in each case (designated system A and B
when warp and weft direction could not be determined) and all
threads of differing colours were tested, i.e. at least two samples
were analysed for each textile.
2.1.1. Danish archaeological textiles
The samples analysed were taken from the textiles found inpeat
bogs on 27 sites, mainly on Jutland peninsula (Fig. 1). The majority
of the finds are now in the collections of the National Museum of
Denmark, but individual finds are also in the museums at Randers,
Viborg, Års, Kolding, Silkeborg and Ålborg. They are all dated to the
Scandinavian Early Iron Age (500 BC–AD 400). Only two of the finds
were previously tested, however using a different method (Walton,
1988).
2.1.2. Norwegian archaeological textiles
The samples come from the finds recovered at the sites of Tegle
and Helgeland in southern Norway (Fig. 1), currently in the
collection of the Stavanger Museum. Only a selection of samples
was provided and analysed, however they should be representative
for these finds. Both finds are dated to the Scandinavian Migration
period (AD 400–575).
2.2. Technique
2.2.1. High performance liquid chromatography
Previous organic dye studies of archaeological samples from
Danish textiles were performed with UV/visible spectrophotometry
after dye extraction, followed by confirmation with paper and thin-
layer chromatography (Walton, 1986, 1988). In the present study,
high performance liquid chromatography (HPLC) was used. For
each component eluting the column at a specific retention time, the
characteristic UV-visible spectra are recorded with the help of
a photo diode array detection system (DAD). Identification of dye
components is done by comparison of both retention time and the
spectral data of the sample with those from a reference database.
Although this technique has proven its efficiency for the
detection of natural organic dyes in archaeological textiles from
a wide historical and geographical context (Cardon et al., 2004;
Hofmann-de Keijzer et al., 2005; Nowik et al., 2005; Szotek et al.,
2003; Vanden Berghe and Wouters, 2004a,b; Wouters, 1998;
Wouters and Rosario-Chirinos, 1992; Zhang et al., 2008), the anal-
ysis of archaeological finds imposes particular challenges. Envi-
ronmental processes before and during excavation, interactions
between the objects of study and other finds in direct or indirect
contact with them, different stages of degradation of the textile or
pseudomorph itself and of the surrounding materials, the mutual
influences of the occurring degradation reaction mechanism are
just some of the major external factors that will have influence on
the actual state of the textiles and dyes.
2.2.2. Improvement of the analytical protocol
The amount of dyes left on archaeological textiles is usually very
low. Preliminary dye analyses on a small set of samples showed that
only very small peaks were found mainly referring to flavonoid dye
components. These tests were done using acidic methanol extrac-
tion, a well-known method for the detection of a wide range of dye
constituents belonging to the main three groups of naturalcolorants,
the anthraquinone, flavonoid and indigoid dyes (Wouters, 1985).
In order to improve the sensitivity of the analysis method with
respect to archaeological bog samples, a second analytical protocol
was applied using acidic methanol extraction, followed by a second
extraction in ethyl acetate (EtAc). Based on previous studies on
archaeological textiles from Verucchio, Italy (700–640 BC) (Vanden
Berghe, 2002) and Bucovina County in Romania (14–15th century
AD) (Petroviciu et al., forthcoming), this method proved to be very
sensitive fordye extraction in verycontaminated samples. Especially
Fig. 1. . Geographical position of the Scandinavian sites.
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–1921 1911
Author's personal copy
for flavonoids, other extraction methods, giving higher extraction
yields and preserving the glycosidic linkages, were evaluatedas well.
Two soft extraction methods using ethylenediaminetetraacetic acid
(EDTA) and formic acid have been reported recently to be very effi-
cient in extracting dyes, while only causing minor or no decompo-
sition of the glycosides (Zhang and Laursen, 2005). The formic acid
method gave a better efficiency for anthraquinone dyes extracted
from silk, while extraction with EDTA was preferable in the case of
flavonoids. The last protocol tested was acidic methanol extraction
followed by a consecutive extraction in dimethylformamide (DMF).
Applied on newly dyed wool samples, as well as on historical wool
textiles from Scottish bog costumes, this method was reported to
give a better efficiency for a lot of flavonoids, indigotin and some
anthaquinones (Surowiec et al., 2006).
3. Experimental
Each dye analysis requires a sample between 0.2 and 0.5 mg.
After pre-examination under binocular to avoid visible contami-
nation, the dyes were extracted from the yarn using one of the
following extraction methods.
3.1. Extraction method 1 (code Acid. MeOH) (Wouters, 1985)
To the sample of yarn, 250
m
l water/methanol/37% hydrochloric
acid (1/1/2, v/v/v) is added. The mixture is heated for 10 min at
105
C in open Pyrex tubes in a heating block. After cooling it is
filtered through a porous polyethylene frit. The clear filtrate is dried
in an evacuated desiccator over NaOH pellets. The dry residues are
taken up in 50
m
l methanol/water (1/1, v/v) and 20
m
l of this solu-
tion is injected for analysis.
3.2. Extraction method 2 (code Acid. MeOH/DMF)
(Surowiec et al., 2006)
To the sample of yarn, 400
m
l water/methanol/37% hydrochloric
acid (1/1/2, v/v/v) is added. The mixture is heated for 10 min at
105
C in open Pyrex tubes in a heating block. After rapid cooling
down under tap water, the extract is dried in an evacuated desic-
cator over NaOH pellets. The dry residues are taken up in 400
m
l
methanol/dimethyl formamide (1/1, v/v) and heated for 5 min at
105
C, followed by rapid cooling down and filtering through
a porous polyethylene frit. The filtrate is evaporated in an evacuated
desiccator over NaOH pellets. The dry residues are taken up in 50
m
l
methanol/water (1/1, v/v) and 20
m
l of this solution is injected in
the chromatograph.
3.3. Extraction method 3 (code Acid. MeOH/EtAc)
To the sample of yarn, 500
m
l water/methanol/37% hydrochloric
acid (1/1/2, v/v/v) is added. The mixture is heated for 10 min at
105
C in open Pyrex tubes in a heating block. After rapid cooling
under tap water, the solution is extracted a second time by adding
1000
m
l ethyl acetate. After decanting of the upper phase, this ethyl
acetate solution is evaporated in an evacuated desiccator over
NaOH pellets. The dry residues are taken up in 50
m
l methanol/
water (1/1, v/v) and 20
m
l of this solution is injected in the
chromatograph.
3.4. Extraction method 4 (code H
2
EDTA) (Zhang and Laursen, 2005)
To the sample of yarn, 200
m
l of 0.001 M H
2
EDTA/acetonitrile/
methanol (2/10/88, v/v/v) solution is added. The mixture is heated
for 30 min at 60
C in closed Pyrex tubes in a heating block. After
cooling down at room temperature the extract is evaporated in an
evacuated desiccator over NaOH pellets. The dry residues are taken
up in 50
m
l methanol/water (1/1, v/v). After centrifuging of the
solution, 20
m
l of upper phase of this solution is taken for injection
in the chromatograph.
3.5. Extraction method 5 (code HCOOH) (Zhang and Laursen, 2005)
To the sample of yarn, 200
m
l formic acid/methanol (5/95, v/v) is
added. The mixture is heated for 30 min at 40
C in closed Pyrex
tubes in a heating block. After cooling down at room temperature
the extract is evaporated in an evacuated desiccator over NaOH
pellets. The dry residues are taken up in 50
m
l methanol/water (1/1,
v/v). After centrifuging of the solution, 20
m
l of upper phase of this
solution is taken for injection in the chromatograph.
3.6. Chromatographic conditions
The HPLC equipment consists of a high-pressure pump (Model
M615, Waters, USA), a photo diode array detector (Model 996,
Waters, USA) and a system for data storage, manipulation and
retrieval (Empower, Waters, USA).
For the extraction methods using acidic methanol alone or in
combination with a second extraction (methods 1–3), the same
chromatographic conditions were applied using a temperature
controlled (20–22
C) Lichrosorb RP-18 column (4.0 125 mm,
5
m
m particle size, VWR, Belgium). Three solvents are used: (A)
water; (B) methanol; and (C) 5% (w/v) phosphoric acid in water. The
elution program is 60A/30B/10C for 3 min, followed by a linear
gradient to 10A/80B/10C for 26min. A flow rate of 1.2 mL/min was
used (HPLC protocol 1).
The mild extraction methods, developed to optimise the detec-
tion of flavonoid glycosides and degradation products (methods 4
and 5), required the development of an adapted analytical protocol.
A monomeric Grace Vydac DE C18 column (3.2 250 mm, 5
m
m
particle size, Grace Devision, BE) was chosen providing very good
separation of both small-molecule analytes as well as high molec-
ular weight molecules such as glycosides. A flow rate of 0.4 mL/min
was used during the 50 min runtime. The solvent gradient was
composed of: (A) acetonitrile for HPLC; (B) water; and (C) tri-
fluoroacetic acid 0.1%. The elution program starts with a linear
gradient for 20 min from 10A/70B/20C to 30A/70B/0C followed by
a linear gradient to 60A/40B/0C for 20 min and an isocratic gradient
for 10 min (HPLC protocol 2).
Identification of the dye components was done by comparison
of the spectral data with the reference spectra in the KIK/IRPA
database (130 references) at the maximum absorbance wavelength
of each peak.
4. Results
4.1. Evaluation of the analytical protocols on archaeological
bog samples
The results of the applied protocols on a small selection of
archaeological bog textile samples are given in Table 1. Limitations
in sample size made it impossible to test all protocols on the same
sample. Considering previous positive experiences with Acid.
MeOH/EtAc extraction on archaeological samples, compared to
Acid. MeOH alone, we chose to focus on the comparison of the first
method with the soft extraction methods. Evaluation of the
different extraction and HPLC methods was not straightforward
considering the minimal remains of dyes left on the samples,
implying that any heterogeneity of the samples could influence the
outcome of the comparison.
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–19211912
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Most of the aglycones were found using the acidic methanol
extraction followed by the ethyl acetate extraction in (MeOH/EtAc).
For specific samples,flavonoids were found only with one of the mild
extractionmethods, but not detected with ethyl acetate. This was the
case with samples 95 from Borremose I and 152 from Krogens Mølle,
where luteolin was only detected using the HCOOH method, while
for samples 115 and 118 from Huldremose I, rhamnetinwas observed
twice, in the warp onlyusing HCOOH extraction and in the weft using
both HCOOH and H
2
EDTA mild extractions. However, also the
opposite occurred. The flavonoids in theHaraldskær sample 13 were
only found by using MeOH/EtAc. The MeOH/DMF method proved to
be most useful for the detection of indigotin (samples 149 and 152,
both from Krogens Mølle) but less efficient for flavonoids.
None of the dye protocols tested on the bog samples resulted in
the detection of glycosides and whatever the applied technique,
components were still detected just above the detection limitof the
analysis. Considering the peak height of the detected dye
components (mainly focussing on luteolin) as well as the colour of
the sample after extraction, best extraction of the dyes was
obtained by using the Acid. MeOH/EtAc extraction and analysis
protocol. A typical example of the outcome of the dye analyses of
a Danish bog textile (97) from Fræer Mose, analysed after HCOOH
extraction using HPLC protocol 2 (Fig. 2A) and after Acid. MeOH/
EtAc extraction using HPLC protocol 1 (Fig. 2A) is given in Fig. 2.
Although a better outcome for flavonoids or indigoids was found
in some occasions respectively using one of the soft extractions or
the MeOH/DMF method, the risk of loosing other categories of
constituents remained very significant with these specific archaeo-
logical samples. None of the investigated methods, applied on this
type of archaeological samples, could lead to a systematic
improvement of the dye analysis.
Considering that acidic methanol extraction followed by the
ethyl acetate treatment turned out to give the best dye extraction,
leading to the detection of both flavonoid as indigoid dyes in
Table 1
Study of different analytical protocols applied on Scandinavian archaeological textiles.
Object ID/site Sample ID/description Codes extraction method Dye component(s) Derivates of Other
Benzoic acid Cinnamic acid
NM C24624
Bredmose
04 dark warp Acid. MeOH/EtAc Luteolin, apigenin X
Acid. MeOH/DMF
NM C25182 Ømark 11 coloured weft HCOOH X
Acid. MeOH/EtAc X X
NM 3707C2
Haraldsær
13 dark warp HCOOH X
Acid. MeOH/EtAc Luteolin, quercetin X
NM C7649
Stockholm
32 light weft HCOOH Luteolin X X
Acid. MeOH/EtAc Luteolin X
NM C26451
Borremose I
95 system A HCOOH Luteolin X X
H
2
EDTA X X
Acid. MeOH/EtAc Unknown 1 wlichen X
NM C26451
Borremose I
96 system B HCOOH X X
H
2
EDTA X X
Acid. MeOH/EtAc Unknown 1 wlichen X
NM 7142A Fræer 97 warp HCOOH Luteolin X X
H
2
EDTA Luteolin X X
Acid. MeOH/EtAc Luteolin, apigenin X
NM C3474
Huldremose II
115 medium warp HCOOH Rhamnetin X X
H
2
EDTA X X Epigallo-catechin
Acid. MeOH/EtAc Unknown 5 þunknown 3 wlichen/
alkannin
XX
NM C3474
Huldremose II
118 medium weft HCOOH Rhamnetin X X
H
2
EDTA Rhamnetin X X
Acid. MeOH/EtAc Unknown 3 wlichen/(alkannin) X X
NM C3477
Huldremose I
144 band Acid. MeOH Indigotin X
Acid. MeOH/EtAc Indigotin, indirubin, luteolin X Ellagic acid
Acid. MeOH/DMF Indigotin, indirubin Ellagic acid
NM D1310I
Krogens Mølle
149 warp, coarse twill HCOOH X
Acid. MeOH X
Acid. MeOH/EtAc X Ellagic acid
Acid. MeOH/DMF Indigotin Ellagic acid
NM D1310I
Krogens Mølle
152 dark twill HCOOH Luteolin X X
H
2
EDTA X X
Acid. MeOH X
Acid. MeOH/EtAc X Ellagic acid
Acid. MeOH/DMF Indigotin Ellagic acid
NM D1310I
Krogens Mølle
153 system 1, tabby HCOOH X X
H
2
EDTA X X
Acid. MeOH/EtAc Indigotin X
NM D12244
Grathe Hede
159 reddish thread,
system 1
HCOOH X
Acid. MeOH/EtAc X
VSM 09374 Elling 174 weft Acid. MeOH X
Acid. MeOH/EtAc Luteolin X Ellagic acid
Acid. MeOH/DMF Indigotin Ellagic acid
NM 7325c Corselitze 179 warp Acid. MeOH/EtAc Luteolin X
HCOOH Luteolin X X
H
2
EDTA Luteolin X X
Extractions coded Acid. MeOH, Acid. MeOH/EtAc and Acid. MeOH/DMF are related to HPLC protocol 1; extraction methods HCOOH and H
2
EDTA to HPLC protocol 2.
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–1921 1913
Author's personal copy
several analyses and that it was the only technique showing
constituents suggesting the use of lichen dyes, the last method was
selected for the analysis of the complete series of peat bog textiles.
4.2. Results of dye analysis of Scandinavian bog textiles
An overview of the identified dye components on the Scandi-
navian bog textiles, for each site, is given in Table 2. The individual
samples are listed in alphabetical order of the sites and according to
the object inventory number,sample number and description of its
colour and function. Radiocarbon dates for the finds are provided in
brackets (Halvorsen, forthcoming; Mannering et al., forthcoming).
In 80% of the analysed samples, traces of one or more dye
components were detected. Small peaks of luteolin were found on
the majority of the samples. Other, more rarely detected flavonoids
were apigenin, quercetin and rhamnetin. Although the actual
colour of the samples is varying from almost black to different
brown and reddish/brown shades, red dye components were very
rare. Alizarin and purpurin were detected in only two textiles.
Indigotin and indirubin were found as well, frequently in combi-
nation with luteolin in the same textile. Since most of these
compounds are not species specific and because dye sources are
usually composed of many different characteristicdye components,
only few of which survived over time in these prehistoric samples,
species identification is hardly possible. The dye results rather
suggest a specific range of dye sources.
4.2.1. Yellow dyes
Luteolin (3
0
,4
0
,5,7-tetrahydroxyflavone) was found in two thirds
of the samples, occasionally in combination with other flavonoids.
Apigenin (4
0
,5,7-trihydroxyflavone) wasdetected seven times, while
a combination of luteolin with quercetin (3,3
0
,4
0
,5,7-pentahydroxy-
flavone) was detected twice. Studies dealing with the photooxida-
tion mechanism of the very light sensitive group of flavonoid dyes
(Ferreira et al., 2002, 2003; Peggy, 2006) have shown that, among
them, the flavones are the most stable constituents. However, the
lack of knowledge about the degradation mechanism of these
constituents in an oxygen and light free, humid environment does
not allow at present any explanation of the predominance of luteolin
as the main flavonoid component found in peat bog textiles. The
preservative qualities of the bog environment, however, may
account for the higher degree of survival of luteolin in bogs
compared to other archaeological contexts.
Possible luteolin-based yellow dye sources in a North European
context are weld (Reseda luteola L.), sawwort (Serratula tinctoria L.),
dyer’s broom (Genista tinctoria L.) or chamomile types (Anthemis
species) (Cardon, 2007; Schweppe, 1993). As, apart from luteolin
and occasionally apigenin, no other characteristic flavonoid
Absorptionunits
(AU, 255nm)
A
B
0,000
0,002
0,004
Minutes
5,00 10,00 15,00 20,00 25,00 30,00 35,00 40,00 45,00 50,00
dhb
phb
dhb’’ cin’ cin’’ lu (Rt 29,3)
259,2
294,7
254
259,2
221,6
282,9 202,9
228,7
278,1
Rt 29,3
259
295
Rt12,5
259
Rt13,8
222
283
Rt 16,4
203
229
278
Rt 18,1
254
349
dhb phb dhb’’ cin’ cin’’ lu
Rt8,5
300 700nm300 700nm300 700nm300 700nm300 700nm300 700nm
AU
0,015
0,020
0,025
0,030
0,035
0,040
Minutes
10,00 12,00 14,00 16,00 18,00 20,00 22,00 24,00 26,00 28,00 30,00
lu (Rt15,2)
Absorptionunits
(AU, 255nm)
wavelength (nm)
200 300 400 500 600 700
251 350
AU
luteolin spectra
Tx97 / Ref.
Fig. 2. HPLC-DAD analysis of warp thread (97) from bog textile from Fræer Mose (110 BC–AD 60): chromatograms (integration at 255 nm) and UV-Vis absorbance spectra after
HCOOH extraction and HPLC protocol 2 (ACN/water/TFA gradient) (A) and after Acid. MeOH/EtAc extraction and HPLC protocol 1 (water/MeOH/H
3
PO
4
gradient) (B); Detected
components: luteolin (lu); 3,4-dihydroxybenzoic acid (dhb) and derivative of dhb (dhb0); para-hydroybenzoic acid (phb) and derivatives of cinnamic acid (cin0, cin00 ).
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–19211914
Author's personal copy
Table 2
Dye components found in Scandinavian Early Iron Age peat bog textiles.
Object ID Sample ID Warp/weft Sample description HPLC-DAD detected dye components Applied extraction(s)
Ålestrup, Denmark (520380 BC)
VMÅ C183(4) 66 Warp Light brown Luteolin 1
VMÅ C183(4) 67 Warp Dark brown Luteolin þapigenin 1
VMÅ C183(4) 68 Weft Light brown Luteolin 1
VMÅ C183(4) 69 Weft Dark brown Luteolin 1
VMÅ C183(6) 70 Warp Dark brown No dyes detected 1
VMÅ C183(6) 71 Warp Light brown Luteolin 1
VMÅ C183(6) 72 Weft Dark brown Luteolin 1
VMÅ C183(6) 73 Weft Light brown Luteolin þapigenin 1
Auning, Denmark (200 BCAD 140)
KHM 233/74 74 Warp Dark brown, pigmented Luteolin 1
KHM 233/74 75 Warp Light brown Luteolin 1
KHM 233/74 76 Weft Dark brown, pigmented Luteolin 1
KHM 233/74 77 Weft Light brown Luteolin 1
Borremose I, Denmark (365116 BC)
NM C26451 95 Warp Dark brown, pigmented Luteolin þunknown 1 (415) 1, 4, 5
NM C26451 96 Weft Dark brown, pigmented Unknown 1 (415) 1, 4, 5
Borremose II, Denmark (48395 BC)
NM C26441 86 Warp Light brown Luteolin 1
NM C26441 87 Weft Light brown Luteolin 1
NM C26441 156 Warp Light brown, shiny Luteolin 1
NM C26441 157 Weft Light brown, shiny Luteolin 1
NM C26442 84 Warp Medium brown, pigmented Luteolin 1
NM C26442 85 Weft Medium brown, pigmented Luteolin 1
NM C26443 90 Warp Light brown Luteolin 1
NM C26443 91 Warp Light brown Luteolin 1
NM C26443 92 Weft Light brown Luteolin 1
NM C26443 93 Weft Light brown Luteolin 1
Borremose III, Denmark (401209 BC)
NM C26454 88 Warp Medium warp Luteolin 1
NM C26454 89 Weft Medium weft Luteolin 1
Borremose V, Denmark (370180 BC)
VMÅ 832 C189 61 Warp Light brown Luteolin 1
VMÅ 832 C189 62 Weft Light brown Luteolin 1
VMÅ 832 C189 63 Sewing thread Dark brown, plied No dyes detected 1
VMÅ 832 C189 64 Sewing thread Light brown, plied Luteolin 1
VMÅ 832 C189 65 Darning thread Light brown Luteolin 1
Bredmose, Denmark (370 BCAD 10)
NM C24623 101 Warp Light brown Luteolin þunknown 2 (422) and unknown 4 (414) 1
NM C24623 102 Warp Dark brown, pigmented Luteolin þunknown 2 (422) and unknown 4 (414) 1
NM C24623 103 Weft Light brown Luteolin þunknown 2 (422) and unknown 4 (414) 1
NM C24623 104 Weft Dark brown, pigmented Luteolin þunknown 2 (422) and unknown 4 (414) 1
NM C24624(1) 1 Weft Dark brown, pigmented Indigotin þluteolin 1
NM C24624(1) 2 Warp Light brown Luteolin 1
NM C24624(1) 3 Weft Light brown Luteolin þunknown 2 (422) 1
NM C24624(1) 4 Weft Dark brown, pigmented Luteolin þapigenin 1, 2
NM C24624(2) 5 Weft Dark brown, pigmented Luteolin 1
NM C24624(2) 6 Warp Light brown Luteolin þa trace of unknown 2 (422) 1
NM C24624(2) 7 Weft Light brown Luteolin þunknown 2 (422) 1
NM C24624 8 Sewing thread Light brown Luteolin þunknown 2 (422) 1
NM C24626 109 Sprang Light brown No dyes detected 1
NM C24627 105 Warp Light brown Luteolin 1
NM C24627 106 Warp Black, pigmented Luteolin 1
NM C24627 107 Weft Light brown Luteolin 1
NM C24627 108 Weft Black, pigmented Luteolin 1
NM C24627 181 Warp Light reddish brown Indigotin 1
Corselitze, Denmark (AD 210410)
NM 7325 a 41 Warp Dark brown, pigmented Luteolin 1
NM 7325 a 42 Weft Dark brown, pigmented No dyes detected 1
NM 7325 b 39 Warp Dark brown, pigmented Indigotin þluteolin 1
NM 7325 b 40 Weft Dark brown, pigmented Indigotinþluteolin 1
NM 7325c 179 Warp Reddish brown Luteolin 1, 4, 5
NM 7325c 180 Weft Reddish brown Luteolin 1
NM 7325x 177 Warp Light brown Luteolin 1
NM 7325x 178 Weft Light brown Indigotin þluteolin 1
Elling, Denmark (380 BCAD 10)
VSM 09374 173 Warp Dark brown, pigmented? Luteolin 1
VSM 09374 174 Weft Dark brown, pigmented? Indigotin þluteolin þellagic acid 1, 2, 3
VSM 09374 175 Sewing thread Dark brown, pigmented Luteolin 1
VSM 09374 176 Sewing thread Light brown Luteolin 1
Fræer, Denmark (110 BC–AD 60)
NM 7142A 97 Warp Light brown Luteolin þapigenin 1, 4, 5
NM 7142A 98 Weft Light brown Luteolin 1
(continued on next page)
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Table 2 (continued)
Object ID Sample ID Warp/weft Sample description HPLC-DAD detected dye components Applied extraction(s)
NM 7142B 99 Warp Light brown Luteolin 1
NM 7142B 100 Weft Light brown Luteolin þapigenin 1
Grathe Hede, Denmark (190 BCAD 10)
NM D12244(2) 128 System A Dark brown, pigmented No dyes detected 1
NM D12244(2) 129 System A Light brown No dyes detected 1
NM D12244(2) 130 System B Dark brown No dyes detected 1
NM D12244(2) 131 System B Light brown Luteolin 1
NM D12244(1) 158 System A Light brown Indigotin 1
182* Indigotin 1
NM D12244(1) 159 System A Reddish brown No dyes detected 1, 4
183* No dyes detected 1
NM D12244(1) 160 System B Dark brown Indigotin 1
184* No dyes detected 1
Haraldskær, Denmark (34742 BC)
NM C37143 23 Sprang Dark reddish brown No dyes detected 1
125* Luteolin 1
NM 3706 21 Warp Light brown Luteolin 1
NM 3706 22 Weft Light brown Luteolin 1
NM 3707 C1 121 System A Light brown No dyes detected 1
NM 3707 C1 122 System A Black, pigmented No dyes detected 1
NM 3707 C1 123 System B Light brown No dyes detected 1
NM 3707 C1 124 System B Black, pigmented No dyes detected 1
NM 3707 C2 12 Warp Light brown No dyes detected 1
17* Luteolin 1
NM 3707 C2 13 Warp Dark brown, pigmented Luteolin þquercetin 1, 4
15* Luteolin 1
19* Luteolin 1
NM 3707 C2 14 Weft Light brown No dyes detected 1
18* Luteolin þellagic acid 1
NM 3707 C2 16 Weft Dark brown, pigmented Luteolin 1
20* Luteolin 1
Huldremose I, Denmark (35041 BC)
NM C3473 169 Warp Light brown Indigotin þluteolin þunknown 5 (324) 1
NM C3473 170 Warp Medium brown, pigmented Indigotin þluteolin þunknown 5 (324) 1
NM C3473 171 Weft Light brown Indigotin þluteolin þunknown 5 (324) 1
NM C3473 172 Weft Medium brown, pigmented Luteolin þunknown 5 (324) 1
NM C3474 114 Warp Light brown Unknown 5 (324) 1
NM C3474 115 Warp Medium brown Unknown 5 (324) þunknown 3 (503)/rhamnetin 1, 4, 5
NM C3474 116 Warp Medium brown, pigmented Unknown 5 (324) þunknown 3 (503) 1
NM C3474 117 Weft Light brown Unknown 5 (324) þunknown 3 (503) 1
NM C3474 118 Weft Medium brown Unknown 3 (503)/rhamnetin 1, 4, 5
NM C3474 119 Weft Medium brown, pigmented Unknown 3 (503) 1
NM C3474 120 Warp Medium brown, thick Unknown 5 (324) þunknown 3 (503) 1
NM C3477 144 Warp Green-brown Indigotin þindirubin þellagic acid þluteolin 1, 2, 3
Huldremose II, Denmark (35030 BC)
NM C3505 110 Warp Light brown Ellagic acid 1
NM C3505 111 Warp Medium brown, pigmented Luteolin 1
NM C3505 112 Weft Light brown Luteolin 1
NM C3505 113 Weft Medium brown, pigmented No dyes detected 1
Karlby, Denmark (200 BCAD 140)
NM D4854 43 Warp Black, pigmented No dyes detected 1
NM D4854 44 Warp Light brown Luteolin 1
NM D4854 45 Weft Black, pigmented Luteolin 1
NM D4854 46 Weft Light brown No dyes detected 1
Krogens Mølle, Denmark (399181 BC)
NM D1310A 24 Warp Medium brown Luteolin 1
NM D1310A 25 Warp Dark brown, pigmented Luteolin 1
NM D1310A 26 Weft Medium brown Luteolin 1
NM D1310A 27 Weft Dark brown, pigmented No dyes detected 1
NM D1310C 28 System A Medium brown Indigotin þluteolin 1
NM D1310C 29 System A Dark brown, pigmented Luteolin 1
NM D1310C 30 System B Medium brown Indigotin 1
NM D1310E 34 Warp Light brown Luteolin 1
NM D1310E 35 Warp Dark brown, pigmented No dyes detected 1
NM D1310E 36 Weft Light brown No dyes detected 1
NM D1310E 37 Weft Dark brown, pigmented No dyes detected 1
NM D1310E 38 Sewing thread Medium brown No dyes detected 1
NM D1310I(1) 149 Warp Light brown Indigotin þellagic acid 1, 2, 3, 4
NM D1310I(1) 150 Weft Light brown Luteolin 1
NM D1310I(3) 151 Warp Dark brown, pigmented No dyes detected 1
NM D1310I(3) 152 Weft Dark brown, pigmented Indigotin þluteolin þellagic acid 1,2, 3, 4, 5
NM D1310I(4) 153 Warp Medium brown Indigotin 1, 4, 5
NM D1310I(4) 154 Warp Dark brown, pigmented Luteolin 1
NM D1310I(4) 155 Weft Medium brown Indigotin 1
NM D 1310K 50 Warp Light brown Luteolin 1
NM D1310K 51 Weft Light brown Indigotin þluteolin 1
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Table 2 (continued)
Object ID Sample ID Warp/weft Sample description HPLC-DAD detected dye components Applied extraction(s)
NM D1310M 185 Warp Medium brown No dyes detected 1
NM D1310M 186 Warp Dark brown, pigmented
NM D1310M 187 Weft Medium brown
NM D1310M 188 Weft Dark brown, pigmented
NM D1310N 52 Warp Medium brown Luteolin 1
NM D1310N 53 Warp Dark brown indigotin þluteolin 1
NM D1310N 54 Weft Medium brown Luteolin 1
Ømark, Denmark (390200 BC)
NM C25182 9 Weft Light brown Luteolin 1
NM C25182 10 Warp Light brown Luteolin 1
NM C25182 11 Weft Light brown, stained No dyes detected 1, 4
Rebild, Denmark (360110 BC)
ÅHM 4608(1) 55 Warp Dark brown, pigmented Indigotin þluteolin 1
ÅHM 4608(1) 56 Warp Medium brown Luteolin 1
ÅHM 4608(1) 57 Weft Dark brown, pigmented Luteolin 1
ÅHM 4608(1) 58 Weft Medium brown Luteolin 1
ÅHM 4608(2) 59 Warp Dark brown, pigmented Luteolin 1
ÅHM 4608(2) 60 Weft Dark brown, pigmented Luteolin 1
Rønbjerg II, Denmark (36050 BC)
NM D2625h 161 Warp Light brown thick Luteolin 1
NM D2625h 162 Warp Medium brown Luteolin 1
NM D2625h 163 Warp Black, pigmented Luteolin 1
NM D2625h 164 Warp Dark brown, pigmented Luteolin 1
NM D2625h 165 Weft Light brown Luteolin 1
NM D2625h 166 Weft Dark brown, pigmented Luteolin 1
NM D2625h 167 Weft Reddish brown Luteolin þapigenin 1
NMD2625h 168 Weft Black, pigmented Luteolin 1
Skærsø, Denmark (350 BCAD 90)
MKH 336 139 Warp Dark reddish brown Alizarin 1
MKH 336 140 Weft Dark reddish brown Alizarin (contamination of warp?) 1
MKH 336 141 Tablet Dark reddish brown No dyes detected 1
MKH 336 142 Tablet Dark reddish brown No dyes detected 1
MKH 336 143 Tassel Red-brown Alizarin þpurpurin 1
Søgårds I, Denmark (35251 BC)
SMS634 A205 199 System A Light brown Luteolin and luteolin-like 1
Søgårds II, Denmark (AD 130–340)
SMS634 A402 78 Warp Medium brown Indigotin 1
SMS634 A402 79 Warp Light brown Indigotin 1
SMS634 A402 80 Finishing cord Dark bluish brown Indigotin þindirubin 1
SMS634 A402 81 Tie cord No dyes detected 1
Stidsholt, Denmark (392204 BC)
NM 18472 132 Warp Dark brown, pigmented No dyes detected 1
NM 18472 133 Warp Medium brown No dyes detected 1
NM 18472 134 Warp Light brown No dyes detected 1
NM 18472 135 Weft Medium brown No dyes detected 1
Stokholm, Denmark (360–50 BC)
NM C7649 31 Warp Light brown Luteolin 1
NM C7649 32 Weft Light brown Luteolin 1, 4
NM C7649 33 Weft Medium brown, pigmented Luteolin 1
Thorup I, Denmark (36050 BC)
VSM 2381 136 Weft Light-medium brown Luteolin 1
VSM 2381 137 Weft Light brown Luteolin 1
VSM 2381 138 Warp Light brown Luteolin 1
Thorup II, Denmark (400-200 BC)
NM C27442 145 Warp Light brown Luteolin 1
NM C27442 146 Warp Medium brown Luteolin 1
NM C27442 147 Weft Light brown 1
NM C27442 148 Weft Medium brown Luteolin 1
Unknown site (400–200 BC)
NM u.nr 82 Warp Dark brown, pigmented No dyes detected 1
NM u.nr 83 Weft Dark brown, pigmented No dyes detected 1
Helgeland, Norway (AD 425535)
S5960a 196 Tablet weave Medium brown Luteolin, quercetin and trace of apigenin 1
S5960a 197 Tablet weave Very light brown Luteolin and luteolin-like 1
S5960c 198 System A Medium brown Indigotin 1
Tegle, Norway (AD 445545)
S4850(1) 189 Warp Medium brown No dyes detected 1
S4850(2) 190 Warp Reddish brown Alizarin and indigotin 1
S4850(2) 191 Weft Reddish brown Alizarin and trace of purpurin 1
S4850(3) 192 Warp Dark brown Alizarin and indigotin 1
S4850(4) 193 Sprang Medium brown No dyes detected 1
S4850(5) 194 Warp Dark brown No dyes detected 1
S4850(6a) 195 Yarn Dark brown No dyes detected 1
1: Acid. MeOH/EtAc; 2: Acid. MeOH/DMF; 3: Acid. MeOH; 4: HCOOH; 5: H
2
EDTA; (): maximum VIS absorbance wavelength of unidentified components; *: second sample
analysed. Remark: luteolin-like component: component with spectral data identical to luteolin but at deviating retention time.
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–1921 1917
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components survived, no further specification of the yellow dye
source is possible.
Rhamnetin (3,3
0
,4
0
,5-tetrahydroxy-7-methoxyflavone), was
detected twice in the scarf from Huldremose I. Rhamnetin is
a characteristic component for dye sources from the Rhamnaceae
family. Many Rhamnus species are among the possible sources.
Some of them are native to Europe, like common buckthorn
(Rhamnus cartharticus L.), while many others grow in Asia
(Schweppe, 1993). They are known under many different common
names, such as Persian, Avignon, yellow, buckthorn, French,
German, Italian, Hungarian, Turkish or Greek berries (Hofenk de
Graaff, 2004; Schweppe, 1993). While not all of the botanical
varieties contain the same exact constituents, they all have the
major light fast component rhamnetin in common. Since antiquity,
berries of different species were used for yellow dyeing. Unripe
berries give a yellow coloration on alum mordanted wool, while
ripe berries produce a green colour and in an overripe state a dark
purple red shade is obtained (Hofenk de Graaff, 2004).
4.2.2. Blue dyes
Indigotin is found in 28 samples from 16 textiles. The isomere
indirubin is found twice together with indigotin. Both are the
characteristic dye components referring to the use of an indigoid
dye source. Theoretically, both indigo (Indigofera or Polygonum
species) and woad (Isatis tinctoria L.) are possible dye sources of
these constituents. However, in terms of historical and geograph-
ical context of the textiles, woad is the most probable one, as the
Central Asian Indigofera-derived dye was not imported to Northern
Europe before the Renaissance period (Balfour-Paul, 1998).
There is only one textile where woad was found to be the only
applied dye source. In the textile fromSøgårds Mose II, both the light
and dark warp threads as well as the finishing cord, all belonging to
the leg wrapper A, were dyed with woad, while the tie cord was
found to be undyed (the weft could not be sampled due to the
intactness of the item). In almost all other textiles, indigotin was
found in combination with the flavonoid dye component, luteolin,
indicating that green may have been the desired colour. Evidenceof
woad dyeing was also found in the analysed samples from Tegle and
Helgeland, where it was detected once alone (sample 198) and twice
in combination with alizarin, hence suggesting an original purple
colour of the warp threads from Tegle (samples 190 and 191).
4.2.3. Red dyes
The antraquinone component alizarin was identified in two
samples belonging to the same textile from Skærsø in Denmark,
and three times in Tegle finds excavated in Norway. These are the
only textile fragments from the whole analysed collection, in which
a red dye source of the Rubiaceae family was identified, referring to
well-known sources such as ladies bedstraw (Galium verum L.),
dyer’s woodruff (Asperula tinctoria L.) or madder types (Rubia
species).
In the warp from the ground weave of the Skærsø find, alizarin
was detected alone, while in the weft only a trace of alizarin was
found. It is impossible to say with certainty that the weft was dyed.
Rather, it is likely that it was undyed or only slightly coloured
compared to the warp. No dyes were found in the threads of tablet-
woven borders. The analysed red tassel however, contained both
alizarin and purpurin, with a relative peak area ratio at 255 nm of
90 alizarin over 10 purpurin.
In the Tegle textiles, alizarin was detected twice together with
indigotin in the warp fringe (sample 190) and the warp from the 2/2
twill textile (sample 192) respectively, while alizarin and a trace of
purpurin were found in the weft fringe thread from Tegle (sample 191).
The presence of alizarin as the principal anthraquinone found,
rather suggests the use of a madder-like type of dye instead of the
more local Galium or Asperula species, which have purpurin as the
major characteristic component (Cardon, 2007).
4.2.4. Other constituents
Characteristic to the chromatograms of all archaeological
samples of this corpus is the presence of the many small peaks,
having no absorbance in the wavelengths of the visible light. A lot of
them are derivates of cinnamic and benzoic acid. They could referto
degradation products of dyes (Ferreira et al., 2003; Peggy, 2006),
fibres or either be related to skins or human remains buried in close
contact with the textile finds. Furthermore, considering that most
of the finds were excavated in the 19th and early 20th century, no
records on their conservation exist, making it possible that these
substances may refer to the conservation agents.
Apart from the identified components, five characteristic
constituents were signalised. Four of them have their maximum
absorption around the range of 400–500 nm, hence suggesting
reddish colouring matters. The UV-Visible absorbance spectra and
retention times of the five constituents are given in Fig. 3. Three of
them could not be identified, while unknown 1 showed high
correlation with the spectral data from the laboratory reference of
yellow wall lichen (Xanthoria parietina L.). For unknown 3, high
similarity is foundwith Scandinavian orchil, with alkannet and with
anthocyanidin glycosides, however the latter falling much earlier in
the chromatogram. Based on both the analytical aspect and on the
historical context of the samples, Scandinavian orchil (Ochrolechia
tartarea L.) would be the most probable source. A probable lichen
purple was detected in one of the 3rd–4thcentury AD textiles from
Slusegård, Denmark (Walton Rogers, 1995,137;Fig. 2).
4.2.5. Ellagic acid
The detection of ellagic acid by chromatographic analysis is
indicative for the presence of tannin material. Tannin containing
plants could have been deliberately used for the conversion of
animal skins into leather, or as a mordant or dye in the textile
dyeing process (Hofenk de Graaff, 2004). On the other hand, one
cannot exclude the influence of the peat bog environment, being
rich of tannin material. In fact the preservative qualities of the bog
environment have been shown to be largely due to the conversion
of the polysaccharide sphagnan, produced by the Sphagnum moss,
into the humic acid, which triggers complex chemical reactions
leading to the tanning of the skins and bodies in the bog (Painter,
1995, 1998).
However, the finding of ellagic acid not systematically, but only
six times, in samples belonging to different textiles and to different
sites of excavation, rather suggests that tannin was applied to the
yarn or textile as mordant together with organic dyes, or as the dye
constituent itself. Black dyeing with tannin in the presence of iron is
a well-known ancient technique (Cardon, 2007, 42–46), but also
other colours can be obtained with the use of tannin alone for
instance to achieve yellow shades (Golikov and Vishnevskaya,
1990). The detection of ellagic acid, three times together with both
luteolin and indigotin, once in combination with luteolin, once
alone and one time together with indigotin, rather refers to its use
as a mordant. As in the two last cases no indication was found of
a mordant dye, it is most likely that this dye did not survive the
burial conditions. Similar situation was reported previously for
several Norwegian and Danish finds (Walton, 1988).
5. Discussion
5.1. Abundance of yellow luteolin containing dye source
Traces of luteolin were found in almost all textiles except the
three textiles where no dye components were found at all, and the
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–19211918
Author's personal copy
textiles from Søgårds Mose II and Skærsø, which contained indi-
gotin and alizarin respectively. This is the first series of archaeo-
logical samples where a flavonoid dye was found so frequently.
The fact that traces of luteolin are so abundantly present in this
collection brings up the question whether we can conclude that all
these textiles were dyed with a yellow dye source, or if the flavo-
noid components are present in the textiles as a result of possible
effect of the bog environment. The following arguments can be
given in favour of the first interpretation.
First, the bogs from which the finds originate include a very
limited repertoire of plant species, consisting mostly of various
moss species of Sphagnum (van der Sanden, 1996, 22), none of
which naturally contain luteolin. The analysis of peat bog samples
taken recently at a bog near Silkeborg in East Jutland, Denmark,
following the same procedure as used for the textiles, did not reveal
any traces of luteolin. Second, apart from luteolin alone, also traces
of luteolin together with other flavonoid dye components such as
apigenin and quercetin were found. The detection of rhamnetin
provides further evidence that flavonoid dyes, other than luteolin
containing ones, can survive peat bog conditions. Finally, luteolin is
not present in two textiles where other dyes were used, the Skærsø
find containing the red dye source from the Rubiaceae family and
the woad dyed Søgårds Mose II find. Based on the present study of
the natural organic dyestuffs in this large Early Iron Age corpus, the
arguments presented above rather support the hypothesis of the
application of a yellow dye source.
For all the textiles that do contain luteolin, it is quite remarkable
that it has been used often in combination with woad dyeing for the
creation of stripes and checked patterns by the use of different
coloured warps and wefts. This is also the case in other European
finds, for example the textiles found in the salt-mines of Hallstatt,
Austria, dating 800–400 BC (Hofmann-de Keijzer et al., 2005),
where luteolin and apigenin, as well as other flavonoids have been
identified often in combination with indigotin and other dyestuffs.
A combination of an unidentified yellow with indigotin was
reported for the Late Roman/Migration period textiles from Blind-
heim, Veiem and Sætrang in Norway and Rovsbjerghøj in Denmark
(Bender Jørgensen and Walton, 1986; Walton, 1988). Luteolin was
also detected in the Gerum cloak, a bog find from Sweden dated
360–100 BC (Franze
´n et al., forthcoming).
5.2. Towards dye technology in Early Iron Age
The detection of dye constituents in the majority of the samples,
despite only being present at trace levels, clearly indicates that most
textiles originally were coloured using plant dyes. Only in the
textiles from Stidsholt and an unknown site both dated between
400 and 200 BC, no evidence of the use of biological dye sources was
found. This however does not indicate that they were not dyed
originally, only that the dyes that may have been present did not
survive over time or are either not detectable by HPLC. A small test
of two sets of samples from the same textiles from Grathe Hede
(samples 158/182, 159/183 and 160/184) and from Haraldskær
(samples 23/125, 12/17, 13/15/19, 14/18 and 16/20) also showed that
dye components are sometimes not detected anymore, most prob-
ably due to the heterogeneity of the dyes remaining on the textiles.
The application of the woad plant for dyeing purposes was rec-
ognised in textile finds from ten Scandinavian bog finds chrono-
logically distributed throughout the Early Iron Age. The oldest
indigotin dyed find is from Rebild, dated between the 4th and the
Unknown 1 (415) Unknown 2 (422) Unknown 3 (503)
Unknown 4 (414) Unknown 5 (324)
218
262
397- 414
Rt 20.3
286
324
Rt 17.8
257
295
415
Rt 19.3 259
287
334
422
Rt 21.6 223
279
503
Rt 22.3
Fig. 3. UV-Visible absorbance spectra and retention time (Rt) of unidentified dye constituents.
Vanden Berghe, T. et al. / Journal of Archaeological Science 36 (2009) 1910–1921 1919
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3rd century BC. It provides evidence for the earliest use of indigotin
in Scandinavia. Until now, indigotin has been identified in five
textiles from Lønne Hede, one textile from Donbæk two textiles
from Hjørring Præstegårdsmark, one textile from Tornebuskehøj
and one textile from Rovsbjerghøj, all Roman Iron Age (AD 1–400)
burial sites in Denmark, as well as several Late Roman/Migration/
Viking Age (AD 300–1050) textiles from burials in Norway (Bender
Jørgensen and Walton, 1986; Walton, 1988). Our findings thus
indicate that the useof woadin Scandinavia can be extendedseveral
centuries back in time. In central and southern Europe, however, the
use of woad goes back to even earlier times. Thus, indigotin has been
identified in the textiles found in the salt-mines of Hallstatt, Austria,
dating 800–400 BC (Hofmann-de Keijzer et al., 2005), in the 8th
century BC garments from the princely burials in Verucchio, Italy
(Vanden Berghe, 2002) and in the 6th century BC princely burial in
Hochdorf, Germany (Walton Rogers, 1999). Recently, indigotin has
been identified in the textiles from Hallstatt dated to the Middle
Bronze Age (1600–1200 BC), making this the earliest instance of
woad use in Europe (Hofmann-de Keijzer et al., 2007).
The first instance of the use of a madder-like dye in the analysed
collection is detected in the Skærsø textile, dated to the 1st century
BC. Madder was not cultivated in Scandinavia during Early Iron Age,
suggesting that the dye or the dyed textile may have been traded
long distance (Walton, 1988). Irrespective of its origin, the Skærsø
textile provides the earliest evidence of madderuse in Scandinavia.
Madder was also found in Late Roman period textiles from Rovsb-
jerghøj and Slusegård in Denmark (Walton, 1988; Walton Rogers,
1995) and Late Roman/Migrationperiod textiles from Tofte, Veiem,
Snartemo V and Evebø/Eide in Norway (Bender Jørgensen and
Walton, 1986; Walton, 1988), which corresponds well to our results
for the textiles from Tegle, Norway. A red dye source from the
Rubiaceae family was also found in two Danish grave finds (Taylor,
1992) and in a tablet-woven band from a tunic found in the grave-
mound at Ho
¨gom in Sweden (Hofenk de Graaff, 2004), all from the
Migration Period (AD 400–520/540). In these fragments however,
purpurin was identified without alizarin, hence suggesting another
Rubiaceae species. The Scandinavian finds thus indicate that
madder became a more common dye source in Scandinavia only
during the Migration period.
Unlike in the case of finds from Hallstatt, Austria (Hofmann-de
Keijzer et al., 2005) and Hochdorf, Germany (Walton Rogers, 1999),
no insect dyes have been identified among the Scandinavian
textiles. This, however, is not surprising, since the presence of these
dyes among the Central European finds is interpreted as a result of
long distance exchange with the Mediterranean areas.
6. Conclusions
Evaluation of different dye extraction and HPLC techniques
made it possible to select the most appropriate analytical protocol
for the archaeological bog samples. The method using acidified
methanol extraction followed by a second extraction in ethyl
acetate extraction was applied for the complete series of peat bog
textiles.
Natural organic dyes found in the Scandinavian textiles repre-
sent the three main categories of natural dyes hence throwing new
light on the use of biological dye sources in Early Iron Age Scan-
dinavia. Among the detected dye constituents are flavonoid dye
components luteolin, apigenin, quercetin and rhamnetin, indigoid
dyes indigotin and indirubin as well as the anthraquinone dyes
alizarin and purpurin. Interesting comparison was also found with
lichen dyes, calling for further study focused on specific local lichen
dye sources and other local sources. Taken into account that only
traces of dye components were detected, it has to be considered
that dyes might have been missed.
The results indicate that the vast majority of the Scandinavian
Early Iron Age textiles recovered from peat bogs originally were
dyed. Already during the Pre-Roman Iron Age (500–1 BC), the
populations in Scandinavia were familiar with the dyeing
technology.
As far as the dyeing technology is concerned, our opinion is that
most fabrics were dyed as finished pieces. The complete staining of
the textiles in the bog does not provide any visual evidence as tothe
dyeing technique. However, in many cases, all threads from the
textiles that are patterned using naturally pigmented wool, tested
positive for the same dyestuffs. Thus, all four samples (two from the
warp and two from the weft) from the Huldremose I skirt, woven in
a checked pattern, contained indigotin, luteolin and unknown 5.
This furthermoreindicates that multiple stage dyeing was per-
formed, demonstrating the familiarity of the Early Iron Age Scan-
dinavians with the dyeing technology and their ability to combine
different dyes. Piece dyeing is an ancient technique, which has been
definitively demonstrated to be the method for the Middle Bronze
Age textiles from Hallstatt, Austria, the earliest European textiles, in
which dyes have been detected (Hofmann-de Keijzer et al., 2007).
Some cases indicate that at least occasionally, yarn was dyed in
order to create patterned textiles. In the Bredmose scarf,the reddish
yarn, creating a grid check pattern tested positive for indigotin,
while the rest of the textile contained luteolin. Sometimes, both
techniques were combined, as in Krogens Mølle Mose skirt, which
had three blue stripes woven into the background and then the
entire piece was coloured with a luteolin-containing dyestuff.
The dyestuffs found in Early Iron Age Danish and Norwegian bog
textiles fit well into the repertoire of dyes used throughout
Northern and Central Europe during the Iron Age. While it is
probable that the dyestuffs were not derived from the same plant
species throughout Europe, many of the sources were similar.
Woad, in particular, is the most likely source for blue colour all over
Europe. Further work is necessary to identify plant sources with
more precision but there can be little doubt that already during the
1st millennium BC there existed a well-developed pan-European
dyeing technology.
Acknowledgements
The authors would like to thank Jenny Dean, Su Grierson and Dr.
Helmut Schweppe for the references offered to the laboratory and
Dr. Beatrice Devia and Marie-Christine Maquoi for the collaboration
in the lab. Sunniva Halvorsen from the University of Bergen and Åsa
D. Hauken at the Stavanger Museum were instrumental in obtain-
ing the Norwegian samples. We also would like to thank the
following colleagues at the Danish museums: Irene Skals, National
Museum of Denmark, Copenhagen; Steen Wulff Andersen, Vejle
Museum, Vejle; Broder Berg, Vesthimmerlands Museum, Års;
Christian Fischer, Silkeborg Museum, Silkeborg; Per Thorling Had-
sund, Nordjyllands Historiske Museum, Ålborg; Margit Petersen,
Viborg Stiftsmuseum, Viborg; John Simonsen, Skive Museum.
Museet for Salling og Fjends, Skive; Ernst Stidsing, Kulturhistorisk
Museum Randers, Randers.
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Book
NOTE: this book can not be shared via Researchgate (also not via private mail) it is for sale via Archetype Publications. This publication is intended to provide a quick overview of well-known dyestuffs that can be found in objects of cultural value in order to contribute to the knowledge of historic textiles and their preservation. Aimed mainly at conservators, conservation students, curators and textile historians, the book presents information on the most relevant dyestuffs used for dyeing textiles, the relation between dyestuffs and organic pigments in paintings and their historical relevance. Emphasis is placed on the combination of historical, technical and scientific knowledge and the way it can be used for the benefit of the conservation of historic textiles. Until the early 1980s the identification of natural dyestuffs was developed and carried out using thin-layer chromatography (TLC) but the development of high performance liquid chromatography (HPLC) opened up greater possibilities and over the past 30 years hundreds of historic textiles have been investigated using this technique. From many investigations carried out for individual museums and institutions, the author has chosen a number of case studies to illustrate both the possibilities and limitations of dyestuff analysis. This title, is published by Archetype Publications Ltd and Abegg Stiftung, Riggisberg, Switzerland (www.abegg-stiftung.ch).