Microchemical Journal 129 (2016) 305309

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Microchemical Journal

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Chemical characterization of ancient liturgical vestment (chasuble) by

Inductively Coupled PlasmaOptical Emission Spectrometry (ICPOES)
Diana Amorello a, Salvatore Barreca b, Maurizio Bruno a, Azzurra Milia a,
Santino Orecchio a,, Alberto Pettignano c
a
Dipartimento di Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche, Universit di Palermo, Viale delle Scienze, I-90128 Palermo, Italy
b
ARPA Lombardia, 20124 Milano, Italy
c
Dipartimento di Fisica e Chimica, Universit di Palermo, Viale delle Scienze, I-90128 Palermo, Italy

a r t i c l e i n f o a b s t r a c t

Article history: This paper presents the chemical characterization of the yarns of an ancient liturgical vestment (chasuble). The
Received 26 April 2016 samples have been analyzed for Al, Ag, Au, Cd, Co, Cr, Cu, Ni, Pb and Zn using amounts always less than 1 mg
Received in revised form 12 July 2016 by Inductively Coupled PlasmaOptical Emission Spectrometry (ICP-OES).
Accepted 12 July 2016
Except a sample, silver is the most abundant element in all the yarns. In the samples containing silver, it ranged
Available online 14 July 2016
from 68 to 97%. Only two samples contain aluminum. Although the investigated chasuble is recorded in the in-
Keywords:
ventory as an artifact of the XV century, a part of the yarns is composed of materials attributed to later period.
ICPOES In fact, the voluntary use of aluminum in metal alloys is due to later periods. A yarn appears silver and apparently
Liturgical vestment could be considered equal to others but does not contain silver. The metallic effect is achieved by using a cheaper
Chasuble metal (lead).
Metals 2016 Elsevier B.V. All rights reserved.
Textile yarns

1. Introduction
A considerable improvement of the knowledge of human civilization
is given from the investigation of historical and cultural heritage by
micro analytical techniques [15]. The use of these techniques also
allows to discriminate between objects with similar form and/or ap-
pearance but prepared with different raw materials or technological
procedures [3,6]. Several researches in cultural heritage eld are
dedicated to the study of ancient textile ornaments [7,8]. The characteri-
zation and provenance studies of these materials are generally performed
by determining their chemical composition. This allows discrimination of
the yarn type and of the procedure used for its preparation, both strictly
related to the historical period.
This paper presents the chemical characterization of the textile yarns
of an ancient chasuble, dated by historians to the fteenth century, but,
considering the type of workmanship and materials used, certainly
dates to the seventeenth or eighteenth century. Another aim of this re-
search is the identication of eventual materials used during previous
restorations.
The chasuble, from Latin casulam, is a liturgical vestment used by the
priest to preside at the Eucharistic Celebrations.
Despite the great interest in the cultural heritage eld, to our knowl-
edge no works are devoted to the composition of ancient liturgical
vestments.
Here we report chemical investigations on an ancient chasuble from
the Palermo Royal Palace (Sicily, Italy) using Inductively Coupled
PlasmaOptical Emission Spectroscopy (ICPOES). The yarn chasuble
samples have been analyzed for 10 elements (Al, Ag, Au, Cd, Co, Cr, Cu,
Ni, Pb and Zn) on the metallic part of the yarn using amounts always
less than 1 mg.
Inductively Coupled PlasmaOptical Emission Spectrometry is one
of the most important elemental techniques for the analytical character-
ization of samples in several elds [911]. This technique has excellent
analytical performances such as high precision, selectivity, low detec-
tion limits. Moreover, it is particularly suitable when the amount of
sample is very small, as in our case, and the components are in trace. Fi-
bers alterations and degradations were studied by the aid of an optical
microscope.
2. Experimental part
2.1. The chasuble

The investigated ancient chasuble (Fig. 1) is registered in the inven-

tory of the Royal Palace of Palermo as pinkish planeta brocade with gold
Corresponding author. and silver braids. The chasuble is an object composed of tissues attribut-
E-mail address: bilancias@libero.it (S. Orecchio). able to early XV century, assembled and decorated with gold and silver

http://dx.doi.org/10.1016/j.microc.2016.07.011
0026-265X/ 2016 Elsevier B.V. All rights reserved.
306 D. Amorello et al. / Microchemical Journal 129 (2016) 305309

Fig. 1. Chasuble.

embroideries, probably added at a later date. The article belongs to the
type of Roman chasubles for the presence of a cross on the recto and col-
umn on the verse (Fig. 1) [12]. The main peculiarity of this chasuble is to
be a multi-material object, consisting almost entirely of silk fabrics and
metallic yarns of different types. For its preparation, the tailor used dif-
ferent techniques and it makes the chasuble unique and of particular in-
terest from the historical and artistic points of view. Tailoring technique
appears quite unique and, to date, similar objects in Sicilian context
were not detected. In particular, the outer side bands of the chasuble
are made with a textured fabric, typical French [12], while the central
area, in correspondence of the cross and column, is occupied by a satin
weave where there are embroidery yarns containing metal wires. The
lateral areas occupied by the French fabric, are enriched with gold and
silver embroideries, recalling the colors of embroidered patches and
by bringing more brightness to the artifact. The chasuble appears the re-
sult of a single project despite the use of different fabrics, probably, in
part recycled.
2.2. Laboratory equipment
All glassware and sample containers were thoroughly washed with
hot HNO3 3% solution followed by rinsing with Milli-Q water. These
were nally kept in the oven at 110 C over night. To avoid contamina-
tions of samples, different glassware and pipettes were used for the
standards and for the samples solutions. Grade A glassware was always
employed.
2.3. Quality assurance
All the analyses of elements in yarns samples were repeated three
times and the relative standard deviation results ranged from 0.7 to
6%. A blank was run up every three samples and demonstrate that the
treatment used for cleaning vessels and asks is suitable to obtain the
quality assurance required in this study. Samples and procedural blanks
were run at the same time.
The reproducibility of the sampling was preliminarily checked by
analyzing for Cu ve samples of the same metallic wire. The standard
deviations on sampling, with respect to that of the analytical process,
were similar (about 8%).
The repeatability, calculated as the relative standard deviation
(RSD%) of three independent measurements of a multi-elemental stan-
dard solution at 50 ngmL1, ranged from 0.4 to 10%. The repeatability
of the whole method, calculated as the relative standard deviation
(RSD%), for three independent analysis of independent portions of the
same yard sample, ranged from 0.5 to 12%. All reported data were
blank corrected.
All the analyses (blank, samples and standards) were carried out at
the two selected wavelengths. The differences between the analita con-
centrations at the two wavelengths were lower than 6%.
As reported in previous papers [13], limits of quantication (LOQs)
were determined as 10 times the noise level of the emission in blank
sample (IUPAC Criterion). LOQs were about 0.2 g.
2.4. Reagents
The reagents used throughout were ultrapure grade (Carlo Erba, Mi-
lano, Italy) and all solutions were prepared in Milli-Q water ( =
18 M cm).
2.5. Samples
Prior to analysis, the metallic parts of the yarns have been separated
manually using a plastic clamp.
Eleven micro fragments of metallic samples from different areas
(Fig. 2) of the chasuble were studied.
2.6. Samples preparation
To perform the ICPOES determinations, from 0.2 to 1 mg of each
sample has been exactly weighed using a microbalance (SCALTEC SBC
22). The sample was initially treated with 1 mL of Suprapur HNO3 69%
(Fluka, Milano) and, successively, with 1 mL of aqua regia (HCl-HNO3
31 v/v) (HCl Suprapur Carlo Erba, Milano) in a Teon capsule, heating
in a water bath. The nal solutions of each sample were transferred in
volumetric asks and the nal volumes were adjusted to 25 mL using
MilliQ water.
2.7. ICPOES analysis
An ICP-OES Perkin Elmer, model Optima 2100 equipped with an
auto-sampler model S10 was used for the elemental analysis of the sam-
ples. Data acquisition and processing were performed using the WinLab
32 software (Perkin Elmer). Operating conditions are listed in Tables 1
and 2.
 D. Amorello et al. / Microchemical Journal 129 (2016) 305309
Fig. 2. Sampling points.
2.8. Calibration curves
Multi-elemental standard solutions were prepared by diluting the
appropriate amounts of two certied standard solutions:
Standard solution 1: multi-element (10 g mL1) ICPMS calibration
standard solution in HCl 10% (VWR, catalog number: 456512A) con-
taining: Au, Hf, Ir, Pd, Pt, Rh, Ru, Sb, Sn, Te.
Standard solution 2: multi-element (10 g mL1) ICPMS calibration
standard solution in HNO3 5% (VWR, catalog number: 456502V) con-
taining: Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, In, K, Li, Mg,
Mn, Na, Ni, Pb, Rb, Se, Sr, Tl, U, V, Zn.
The range of concentration of the calibration curves was between 5
and 2500 g L1.
The ICPOES analysis of all the elements was performed in axial
viewing mode. The quantitative determinations were performed at
two different spectral lines for each chemical element (Table 2). The
analyses of the standard solutions were replicated every 6 samples. Be-
tween two successive samples a 30 s washing was settled in order to
eliminate memory effects.
3. Results and discussion
The silver and golden yarns are characterized by a core of silk, while
the metallic part (alloys), in most cases, are composed, from different
amounts of silver, gold, and copper. A total of 11 yarn samples were an-
alyzed by about 350 ICP-OES determinations of single elements. The
analita percentages with respect to the total weight of elements in
each sample are shown in Fig. 3. The results reported in this paper
have been calculated considering the average concentrations calculated
from the intensities at the two selected wavelengths. The differences
between the metal concentrations at the two wavelengths were always
less than 6%.
Table 1
ICP-OES operating conditions.
RF power (W) 1300
Sample uptake ow rate (mL/min) 1.5
Gas ow rates (L/min) Auxiliary: 0.2;
Nebulizer: 0.8;
Argon: 15
Viewing mode Axial
307
Table 2
Wavelengths used for elemental determinations by ICP-OES.
Element Wavelength 1 (nm) Wavelength 2 (nm)
Al 396.153 308.215
Ag 328.068 338.289
Au 267.595 242.795
Cd 228.802 214.440
Co 228.616 238.892
Cr 267.716 205.560
Cu 327.393 324.752
Ni 231.604 221.648
Pb 220.353 217.000
Zn 206.200 213.857
Silver is the most abundant element in all the samples, except sam-
ple n1. In the samples containing silver, it ranged from 68 to 97% (Fig.
3). Only two samples (n3, n10) contain aluminum. The composition
of the sample n1 differs from the other for the large lead and cadmium
percentages and it is the only yarn in which the silver is absent. In par-
ticular, in the other yarns cadmium is only present at trace levels. In
some points of the sample n2, the gold plating is missing (Fig. 4) re-
vealing the underlying silvery surface, therefore, it is conceivable that
a layer of gold (about 10%) was applied on the surface of a silver alloy.
Regarding the appearance, the yarn n3 is similar to n2 and is constitut-
ed by a core of yellow silk on which is wound a spiral gold color. Despite
the similar form of the two metallic yarns (at section), the chemical
composition is different. In particular, sample n3, unlike the previous
one, contains about 13% of Al. The optical microscope examination of
the yarn n4 (sampled from the central area of the chasuble, cross and
column), showed shallow oxidation. This yarn is applied to the embroi-
dery on the fabric and is a curly type yarn: the metal foil is wound in a
spiral around a core of white silk. The silver percentage is greater than
90% and copper, lead, chromium and aluminum are present at trace
levels. The absence of gold is compatible with the color of the yarn.
The yarn n5, also in this case, applied to the embroidery on the
manufactured article, contains a metal foil. In some points, the foil is
much oxidized and shows a dark layer on the silver surface. Silver per-
centage is about 97% and Cu and Pb are present at trace levels. As the
previous sample, the yarn n6 has been taken from embroideries with
metallic elements with a at section. In this case, the yarn appears gold-
en. Silver exceed 90%, while gold is present to about 5% together with
small amounts of copper and lead. Even in this case, the quantity of
gold and silver are compatible with the hypothesis of browning of the
silver alloy foil. The yarn n7 is a curly type, it is not pointed in embroi-
dery but is part of the fabric. The sample n7 has very different appear-
ance than the previous ones but the chemical composition is similar to
that of most of the yarns. We can assume that it has been produced in
different places and/or at different times than the other yarns. There-
fore, being the metallic wire an integral part of the fabric, the yarn can
be attributed to the French production. The elements found are silver
(87%), gold (6.4%), copper (0.71%), lead (3.3%). The remaining part
(less than 5%) consists of cadmium, nickel, chromium and aluminum.
By its silvery appearance and from the analysis of a microphotograph
of the sample (Fig. 5) we exclude the presence of a golden layer. In
this case, gold is part of the alloy which constitutes the metallic wire.
Also in this case, the yarn n8 is part of the fabric. Therefore, it can be at-
tributed to the French production. It is made from a metal foil wrapped
around a core of white silk and has a much thinner diameter than the
other samples. The elemental composition is very similar to that of the
previous sample. The sample n9 is a thin yarn and has been used to
sew golden metallic elements to the fabric. Like the other samples, it
is made by winding a metal foil on a yellow silk core. Sample n9 con-
tains silver (96%), copper (1.4%), lead (1.2%). The remaining part (less
than 2%) consists of cadmium, nickel, chromium and aluminum. The
sample n10 was taken by the gallon applied to the neckline of the cha-
suble. The core of yellow silk gives golden effect to the gallon. By the
308 D. Amorello et al. / Microchemical Journal 129 (2016) 305309

Fig. 3. Elements distribution (%) in yarn samples.

Fig. 4. Sample n2.

microphotographs are not evident wires or plates of gold to the yarn
surface. The golden gallon was realized with materials of low quality
and not containing gold. The materials that compose this sample are
not attributable at the time of execution of the chasuble. Gallon
shows many endings performed carelessly. Sample n10 contains
Ag (68%), Al (15%), Au (3.0%), Cu (2.0%), Pb (5%), Cr (1.1%) and Ni
(1.2%). The other elements are less than 1% each. The chemical com-
positions of the samples n10 and n3 are similar. Compared to all
other samples containing silver, the lowest precious metal percentage
was offset adding aluminum to the alloy. The yarn n11 appears very
oxidized. The metal foil has color tending to dark gray. The metal part
of this yarn is mainly composed of silver (93%), gold (2.5) and copper
(1.5).
In all the samples containing silver except n7, the ratios Cu/Ag are
almost constant (0.020 0.005). It does not seem reasonable to associ-
ate this element to impurities of copper in silver. This correlation is in
good agreement with the different metal wires which were all prepared
from commercial silver alloy, having generally a purity of about 98%.
It is important to consider that three samples (having the same
color) (n4, n5, n9) taken from the different areas of the chasuble,
do not contain gold but show similar composition.

4. Conclusions

To date, according to our knowledge, an analytical approach to the

study of ancient yarns with metallic cores is absent. In this study, a
total of 11 yarns micro samples (0.21 mg) from an ancient chasuble
manufactured in Sicily and restored in different times, were investigat-
ed. In this study, only the ICP-OES technique was used to investigate the
elemental composition on the micro samples. One of the advantages of
the use of ICP-OES for this characterization is the better detection power
Fig. 5. Sample 7 (200). attained, resulting in much improved limits of quantication, which can
 D. Amorello et al. / Microchemical Journal 129 (2016) 305309
be particularly relevant for elements that are present at trace levels in
micro samples object and material relating to cultural heritage.
Although the investigated chasuble is recorded in the inventory as
an artifact of the XV century, a part of the yarns is composed of materials
attributed to later period. In fact, the voluntary use of aluminum in
metal alloys is certainly to be dated around the middle of 1800.
Silver yarns are placed in the internal areas of the chasuble and alter-
nate to the bottom pinkish satin, creating chiaroscuro effects. Silver
yarns are of two different types: the largest (curly type) consisting of
a metal foil wrapped around a silk core consists of two twisted yarns
which give the characteristic appearance corrugated; the smallest
yarn is also characterized by a core consisting of a single silk yarn (not
twisted) around which is wound a metal foil.
A yarn (n1) appears silver and apparently could be considered
equal to others but does not contain silver. The metallic effect is
achieved by using a cheaper metal (Pb).
Acknowledgments
This work was performed thanks to a nancial source from the Uni-
versity of Palermo (ex 60% 2007). The data and information reported in
this publication do not depend on the activities of ARPA Lombardia,
which therefore cannot in any event be held responsible for the con-
tents of the publication, and the conclusions by the authors.
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