Journal of Cultural Heritage 13 (2012) 413–418

Available online at

www.sciencedirect.com

Original article

Accelerated hydrothermal degradation of fibres of Phormium tenax (New Zealand

flax)
Roderick James Weston a , Gerald J. Smith a,∗ , Suzanne M. Scheele b , Stephen H. Williams a
a
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington 6140, New Zealand
b
Landcare Research, P.O. Box 40, Lincoln 7640, New Zealand

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

Article history: Solid-phase microextraction (SPME)–gas chromatography (GC)–mass spectrometry (MS) has been
Received 13 July 2011 applied to the analysis of acetic acid and furfural that are emitted from the fibres of Phormium tenax
Accepted 17 November 2011 (Xanthorrhoeaceae) [New Zealand flax] during degradation. Accelerated hydrothermal ageing of fibres
Available online 27 January 2012
of the Ruawai cultivar of P. tenax for 55 days at 70 ◦ C resulted in the production of acetic acid at a level
greater or equal to 1.65 mg g–1 fibre. This corresponds to only 8.5% of the acetyl groups present in the
Keywords: fibres. These groups are an important source of acetic acid, which is capable of damaging the fibres. The
Accelerated hydrothermal ageing
rate of production of acetic acid suggests that a heritage object made from the fibres of P. tenax, that
Phormium tenax
Acetic acid
was stored in damp ambient conditions, would undergo significant deterioration after a relatively short
Furfural period. Other volatile products released during ageing included furfural, a series of short to medium chain
Aliphatic aldehydes aliphatic aldehydes that were derived from the oxidation of long chain unsaturated fatty acids on the
Nor-isoprenoids fibres and a small group of products that were derived from carotenoids. The levels of furfural were deter-
mined to be approximately 0.75% of the potential production but at these levels, furfural could contribute
to unpleasant odours from unventilated items. Fibres from six cultivars of P. tenax were found to release
acetic acid and furfural all at the same rate. The levels of acetic acid that can be generated from these
fibres are sufficiently high that low moisture levels and continuous change of air is required to minimize
degradation of cultural objects that are made from these fibres and displayed in museum halls.
© 2011 Elsevier Masson SAS. All rights reserved.

1. Introduction investigate the chemistry of this degradation so that means to slow

Over the past decade, several groups have established methods
for monitoring the degradation of paper and cloth that constitute
a significant proportion of organic cultural materials. In particu-
lar, analyses of the VOC that arise from archived documents have
been performed widely [1,2] and HS–SPME coupled with combined
GC–MS has been developed as an especially useful technique for
this purpose [3]. Much of the published work has been applied to
paper and books [4–8].
In New Zealand, the indigenous Maori people wove objects tra-
ditionally from the fibres derived from New Zealand flax, Phormium
tenax (Xanthorrhoeaceae), which is known to Maori as Harakeke.
Many of these objects, including museum exhibits, are showing
signs of deterioration and the purpose of the present work was to
Abbreviations: DVB, Divinylbenzene; GC, Gas chromatography; HS, Head space;
MS, Mass spectrometry; PDMS, Polydimethylsiloxane; SPME, Solid phase micro-
extraction; SIM, Single ion chromatogram; TIC, Total ion chromatogram; VOC,
Volatile organic compound.
∗ Corresponding author. Tel.: +644 463 5547; fax: +644 463 5241.
E-mail address: gerald.smith@vuw.ac.nz (G.J. Smith).
or arrest this process might be established.
The biosystematics, chemistry, ecology, cultural and economic
uses of P. tenax is described by Wehi and Clarkson [9] and use of the
fibres for weaving, is described by Puketapu-Hetet [10]. Traditional
dyes that are used for textiles made from these fibres, are described
by Te Kanawa et al. [11] and accounts of the degradation of these
dyed materials are given by Moore et al. [12] and by Daniels [13].
Throughout its natural range, P. tenax has considerable genetic
and morphological variability [14,15]. Maori selected the fibre from
leaves of wild forms of the plant for specific purposes such as
making garments, fine cloaks, baskets, mats, nets, cordage and wall-
panelling. To this end, they maintained favoured genetic forms
in cultivation. The fibre that is extracted from the different culti-
vars, has varying properties of yield, length, linear density, softness,
colour and durability. The national New Zealand Flax Collection,
held at Landcare Research, Lincoln, New Zealand has over 50 of
these traditional, named weaving cultivars. Several cultivars of
P. tenax with different fibre properties [14,16–18] were selected for
this work, to determine whether the observed degradation prod-
ucts or the rate of degradation differed with the cultivar.
In addition to their physical properties, the chemical composi-
tion of fibres of unspecified cultivars of P. tenax has been reported.

1296-2074/$ – see front matter © 2011 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.culher.2011.11.006
414 R.J. Weston et al. / Journal of Cultural Heritage 13 (2012) 413–418

Turner [19] found that P. tenax fibres have a cellulose content (45%) Table 1
Degradation products from fibre of the Ruawai cultivar of Phormium tenax.
that is lower than that of other common textile fibres and a hemicel-
lulose content (30%) that is correspondingly higher. In comparison, Component Retention Product Abundance (% of TIC)
the cellulose and hemicellulose content of sisal is 66% and 12% while Time
(minutes)
that of cotton is 83% and 6% respectively [19]. Spiegelberg reported
that the tensile strength of a fibre increases as the proportion of 1 week 2 weeks
hemicellulose increases [20]. Phormium fibres have a high hemicel- 1 1.55 Acetaldehyde 0.9
lulose content compared with other natural fibres, explaining why 2 1.69 Acetone 2.9 11.0
P. tenax fibre was a valuable raw material for the textile industry 3 2.07 Acetic acid 3.6 14.1
[21]. Additionally, the hemicellulose of P. tenax fibres was deter- 4 2.22 2-Methylfuran 9.6
5 3.06 Pentanal 2.1 1.8
mined to consist largely of a xylan [22], which is significant in the 6 4.63 Hexanal 15.4 5.1
present study as 1,4-xylose linkages are more reactive and suscep- 7 5.23 Furfural 3.7
tible to hydrolysis than the 1,4-glucose linkages in cellulose. The 8 6.48 Heptanal 3.9 0.6
xylan content of P. tenax fibres was determined by Frieser [23] to 9 7.08 ␣-Pinene 1.9
10 7.62 Benzaldehyde 1.9
constitute 24% by weight of the fibres which is considerably more
11 7.97 6-Methyl-5-hepten-2-one 2.9 2.6
than that of linen and hemp (4%). These data also indicate that a 12 8.30 Octanal 8.8 3.1
xylan constitutes 80% of the hemicellulose component of P. tenax 13 10.00 Nonanal 17.8 10.5
fibres. Furthermore, Newman et al. [24] found that the hemicel- 14 10.67 2,6,6-Trimethylcyclohex-2- 0.5 0.7
lulose of P. tenax fibres possesses some 6.3% by weight of acetate en-1,4-dione
15 10.95 Octanoic acid 1.3
groups, a fact that is significant due to the quantity of acetic acid
16 11.59 Decanal 5.4 2.7
that these groups potentially can generate and that can contribute 17 12.42 Nonanoic acid 1.2 2.9
subsequently to degeneration of the fibrous material. In a museum 18 12.78 1,1,4a-Trimethyl- 0.7
environment, this volatile product is a hazard, not only to the host 3,4,4a,5,6,7-hexahydro-
(1H)-naphthalen-2-one
fibre, but also to neighbouring objects that are vulnerable to degra-
19 14.12 Damascenone 1.6 0.9
dation by acids. 20 14.52 Damascone 0.7 0.4
The aim of this work was to examine the volatile products 21 14.97 6,10-Dimethyl,-5,9- 0.7 0.8
that arise from P. tenax fibres during accelerated hydrothermal undecadien-2-one
degradation, by HS–SPME and GC–MS, to determine whether the
degradation was related to the varietal types and their physical
properties. Additionally, the results can also be compared with
similar work that has been carried out on paper and books [4–8]. fibre and the syringe were then withdrawn from the vial and the
sample was desorbed in the GC injector port at 250 ◦ C for 1 minute.

2. Methods and materials

2.2.3. Gas chromatography and mass spectrometry
HS samples were analysed on a Shimadzu QP2010 Plus GC–MS
2.1. Materials
instrument, which incorporated a Restek Rtx-5Sil MS column,
30 m × 0.25 mm × 0.25 ␮m. The carrier gas was helium which was
Six cultivars of P. tenax [14] were selected for this work: Tapa-
split 20:1 and the column gas flow was 1.2 mL min–1 . The GC injec-
mangu, Ruawai, Ruapani, Whareongaonga, Ngaro and Makaweroa,
tor was held at 250 ◦ C and the GC–MS interface at 300 ◦ C. The
all of which were provided by Landcare Research, Lincoln, New
column was held at 40 ◦ C for 2 min and then raised to 300 ◦ C at
Zealand. They were chosen because the surface layer of wax and
10 ◦ C min–1 and then held there for 5 minutes. Mass spectra were
chlorophyll can be easily mechanically separated from the leaves
recorded at 70 ev from m/z 36–600 at a rate of one scan every
[14] and their fibre is used traditionally for weaving. The recent
0.3 seconds. For quantitative work, SIM were extracted from the
genetic work of Scheele and Smissen [15] indicated that the Rua-
TIC, integrated and the levels of acetic acid and furfural were then
pani and Makaweroa cultivars were genetically identical but the
calculated by reference to the added standard of dioxane.
other selected cultivars were spread widely over their genetic tree.

2.2. Methods
2.2.1. Ageing
P. tenax fibres (300 mg) were cut into small sections (∼ 5 mm)
and placed in a vial (20 mL) which was closed with a Teflon seal
within a screw-cap. Water (2 mL) was added to the vial, which was
then capped and placed in a thermostatically controlled oven at
70 ◦ C for several weeks. HS samples (see below) were removed at 1
week intervals. For quantitative work, a solution of 1,4-dioxane (12
mg) in water (100 mL) was prepared and then 2 mL of this solution
was injected to the closed vial (instead of pure water, as above) as
an internal standard.
2.2.2. Head space adsorption and sample desorption
The sample vial was removed from the oven and placed in a
water-bath at 50 ◦ C for 30 minutes. A Supelco SPME syringe, which
included a 50/30 ␮m fibre coated with DVB/carboxen/PDMS, was
inserted through the seal of the vial, the fibre was extruded and the
HS was adsorbed onto the fibre for 1 hour at 50 ◦ C. The adsorbent
3. Results
The VOCs in the HS above wet fibres of the Ruawai culti-
var of flax during accelerated hydrothermal ageing are listed in
Table 1. Most of the major components in Table 1 were aliphatic
aldehydes, which constituted 53% of all the VOCs that were
detected in the TIC. Other products that were detected, included ␣-
pinene, and several products that were derived from carotenoids,
viz. 6-methyl-5-hepten-2-one, 6,10-dimethyl-5,9-undecadien-2-
one, damascenone and damascanone.
After a total of 2 weeks accelerated ageing, the most obvious
change in the composition of the VOCs was the increase in abun-
dance of acetone from 2.9 to 11.0%, acetic acid from 3.6 to 14.1%
and furfural from 0 to 3.7%. Simultaneously, the abundance of the
major aldehydes that were observed after ageing for 1 week had
decreased; hexanal from 15.4 to 5.1% and nonanal from 17.8 to
10.5%.
To establish whether acetic acid production was related to the
plant cultivar and whether furfural also was produced, samples
of fibre from five other P. tenax cultivars were examined and the
 R.J. Weston et al. / Journal of Cultural Heritage 13 (2012) 413–418 415

Table 2
The percentage of acetic acid and furfural in the mixture of volatile organic compounds (VOC) in the head space (HS) above wet fibres of cultivars of Phormium tenax after
one, two and three weeks accelerated hydrothermal ageing.

Cultivar Component After 1 week After 2 weeks After 3 weeks Change(Week 1 to 2) Change(Week 2 to 3)

Ruawai Acetic acid 45.2 65.5 68.8 +20.3 +3.3

Furfural – 6.2 8.2 +6.2 +2.0
Ruapani Acetic acid 62.9 74.0 73.4 +11.1 –0.6
Furfural – 9.1 15.6 +9.1 +6.5
Makaweroa Acetic acid 44.1 59.1 57.8 +15.0 –1.3
Furfural – 12.7 22.0 +12.7 +9.3
Whareonga Acetic acid 52.8 67.7 66.6 +14.9 –1.1
Furfural – 9.8 16.0 +9.8 +6.2
Ngaro Acetic acid 58.0 77.8 74.2 +19.8 –3.6
Furfural – – 11.1 – +11.1
Tapamangu Acetic acid 50.9 70.6 70.5 +19.7 –0.1
Furfural – 6.5 10.4 +6.5 +3.9

duration of the hydrothermal ageing was extended to 3 weeks. All
the variables in the hydrothermal ageing were kept constant so
the proportion of acetic acid in the HS sample could be used as a
relative measure of the production of acetic acid from the cultivars
examined (Table 2).
1,4-Dioxane was selected as an internal standard for quanti-
tative determination of the production of acetic acid and furfural
because it is chemically inert, volatile, it has a retention time close
to that of acetic acid and furfural and does not overlap in the
chromatogram, with other volatile components from the fibre. The
initial concentration of the dioxane that was added to the sam-
ple vial was used to quantitatively determine the production of
acetic acid and furfural that were generated from the fibre of the
Ruawai cultivar during an ageing experiment and the results for
these experiments are shown in Fig. 1. For this purpose, SIMs of
the molecular ions (m/z 60 for acetic acid; m/z 82 for methyl-
furan and m/z 96 for furfural) were extracted from the TIC and
then the integrated peaks were compared with that of dioxane
(m/z 88). In similar experiments with paper, Łojewski et al. [25]
determined absolute values for furfural production, with exter-
nal standard solutions of furfural that were aged under the same
conditions as the paper.
an indication of changes occurring to the P. tenax fibres during
hydrothermal ageing.
Ramalho et al. [26] recently determined the rates at which
selected VOCs were emitted from paper (derived from either cot-
ton or wood-pulp) in a sealed tube. The papers were conditioned at
23 ◦ C and 50% relative humidity and then placed in the tube which
was heated at 100 ◦ C for 30 days. They found that acetic acid and fur-
fural were the major products emitted from the wood-pulp paper.
Of the VOCs measured, acetone, acetic acid and furfural reached
a maximum rate of emission after 15 days, while formaldehyde
and acetaldehyde reached their maximum emission rates more
rapidly, after 5 days. Furthermore, the emission rates for these
VOCs were different: acetic acid and furfural at ∼ 4.8 ␮g g–1 paper
h–1 , formaldehyde and acetaldehyde at ∼ 0.7/␮g g–1 paper h–1 and
acetone at 0.4 ␮g g–1 paper h–1 .
Results from the present work given in Tables 1 and 2 show
that acetone and acetic acid are the major VOCs emitted from
P. tenax fibres after 14 days of hydrothermal ageing under the condi-
tions described. The rapid increase in acetone from P. tenax fibres is
notably different from that observed for wood-pulp derived paper
and suggests that acetone has arisen possibly from a source other
than cellulose.

4. Discussion 4.1. Acetone

After hydrothermal ageing for 2 weeks, a considerable increase The metabolic origin of acetone in plants is currently unclear
in the proportions of acetone, acetic acid and furfural, relative to [27]. A recent view is that it is derived from pyruvic acid which in
the aldehydes, was observed. Each of these three components is turn is generated from the glycolysis (scission) of the glucose units
of cellulose. Both acetaldehyde and acetic acid also can be generated
from pyruvic acid in plants by decarboxylation. The formation of
2.5
Producon of Acec acid and Furfural acetone follows the same pathway but is accompanied by reaction
with me with a methyl transferase. Pyruvic acid can also be converted into
acetoacetic acid which will decompose spontaneously to produce
Mass VOC (mg g-1 fibre)

2 acetone.
Acetone could also be regarded as the final product of the oxida-
tion of isoprenoids, particularly of the carotenoids. Products from
1.5 the degradation of carotenoids were detected in this work and if
acetone also arises in this way, then its abundance in the HS above
aged fibre suggests that carotenoids and other lipid material should
1
be removed from the fibre before it is used so that unpleasant-
smelling volatile aldehydes and acetone are not emitted from the
0.5 fibres in warm, damp conditions. Furthermore, aldehydes oxidise
readily in air to carboxylic acids which, along with acetic acid, will
contribute to undesirable hydrolysis reactions.
0
0 10 20 30 40 50 60
Days 4.2. Aliphatic aldehydes
Acetic acid Furfural
Aliphatic aldehydes are the most abundant VOCs in the HS above
Fig. 1. Quantitative levels of acetic acid and furfural that were generated from fibres the fibres of the Ruawai cultivar of P. tenax, after hydrothermal age-
of the Ruawai cultivar of Phormium tenax, during accelerated hydrothermal ageing. ing for 1 week. The short-chain aldehydes arise from oxidation of
416 R.J. Weston et al. / Journal of Cultural Heritage 13 (2012) 413–418
the olefinic bonds in long chain fatty acids, catalysed by lipoxyge-
nase enzymes and ferrous ions [28]. Accordingly, nonanal, from the
oxidation of oleic acid and hexanal, from the oxidation of ␻-6 fatty
acids were the major products observed. In a study of the aldehydes
that are present in museum atmospheres, Fenech et al. [2] found
that formaldehyde and acetaldehyde were the major aldehydes
present. Hexanal was also detected, but at lower levels.
In their work on the degradation of paper, Strlič et al. [5]
proposed that fatty acids originated from the rosin used to size
(water-proof) paper. In the present case, however, fibres were
obtained from a monocotyledonous angiosperm and it is unlikely
that such plants contain rosin esters. It is possible that residual lipid
material from the surface layers of the leaves was bound physically
to or present adventitiously in the polysaccharide fibres. However,
since the surface wax and chlorophyll layers of the leaves were
mechanically separated from the fibres used in this work, a more
likely origin is from lipopolysaccharide material in which the lipids
are chemically bound to the fibres. The only solvent extractive
materials that have been isolated from P. tenax leaves to date are
triterpenoids [29] and coumarins [30], and aldehydes are unlikely
to have been produced from these classes of natural product.
4.3. Nor-isoprenoids
The other group of volatile products observed, components 11,
14 and 21 (Table 1) were nor-isoprenoids, very probably derived
from carotenoids [31]. As was the case for the fatty acid precursors
of the aldehydes, the precursor carotenoids may be bound to the
fibres and then the volatile products formed by enzymatic reactions
and oxidation of the carotenoids during the hydrothermal ageing
process. Of special note, was the group of four C-13 nor-isoprenoids
[30–33] that included damascenone and damascone. The latter two
components are important components of the perfume of roses and
aroma of grape and other fruit juices [32–34] and have also been
isolated from the juice of cacti and the derived “Tequila” [35]. The
cactus, Agave tequilana and P. tenax both belong to the Asparagales
order of plants and while somewhat taxonomically distant from
each other, chemical extractives in common might be expected to
occur in both plants.
4.4. Acetic acid
Acetic acid arises from hydrolysis of the acetate groups that are
attached to pendant sugars along the hemicellulose chain of plant
fibres and once released the acetic acid can catalyse further hydrol-
ysis of the acetate groups and ultimately also catalyse hydrolysis
of the xylan chain. In this way, acetic acid production is a major
cause of the degradation of materials made from fibres that have
high hemicellulose contents, such as P. tenax.
It is apparent from Fig. 1 that the production of acetic acid
increased monotonically over the experimental period of 55 days
and all cultivars produced acetic acid with similar kinetics. Ramalho
et al. [26] reported similar results for the production of acetic acid,
after hydrothermally ageing paper for a period of 15 days.
4.5. Furfural
As shown in Table 2, furfural was produced over the experimen-
tal period by all the cultivars of P. tenax, and the yields were still
increasing after 3 weeks of hydrothermal ageing. This behaviour
was expected as the carbohydrate components of the fibre would
continue to produce furfural [7] until all the hemicellulose was
degraded. Ramalho et al. [26] also demonstrated that when paper
is aged hydrothermally, the production of furfural, like acetic
acid, increased over a period of 15 days. The data presented in
Table 2 suggested that there was little difference between any of
the cultivars in their production of acetic acid and furfural, which
implied that the structure of the hemicellulose in each cultivar
was very similar.
4.6. Quantitative determination of acetic acid and furfural
production during accelerated hydrothermal ageing
The production of acetic acid and furfural began without any
latent period and continued over the experimental period of 55
days, to values of 1.65 mg g–1 fibre and 1.85 mg g–1 fibre respec-
tively (Fig. 1). The curves in Fig. 1 indicated that the rates of
production of acetic acid and furfural increased with time.
In related work, Ramalho et al. [26] found that after 15 days
at 100 ◦ C, the rates of production of acetic acid and furfural
from paper reached a plateau of 4.82 ␮g g–1 h–1 and 4.72 ␮g g–1
h–1 respectively. After 15 days, these data translate to 1.74 mg
g–1 for acetic acid and 1.70 mg g–1 for furfural. For P. tenax, the yields
of acetic acid and furfural observed after 15 days were 0.34 mg
g–1 and 0.21 mg g–1 respectively. The lower yields of acetic acid and
furfural that were observed for P. tenax, when compared with those
recorded by Ramalho et al. for paper [26], were probably due to the
elevated accelerated ageing conditions used in that study.
The value observed in the present work for the production of
furfural after 30 days (650 ␮g g–1 ) was 15 times greater than that
recorded (43 ␮g g–1 ) by Łowjewski et al. [25] from a similar exper-
iment with paper. The higher value in the present case may have
been due to the high xylan content of P. tenax fibres.
The yields of acetic acid and furfural in this work were small
when compared with the potential yield of acetic acid and furfural
from P tenax fibres. The acetate content of P. tenax fibres is 6.3%
w/w of the hemicellulose [24], which in turn is 30% of the fibre [19].
These data suggest the potential acetic acid production was 19 mg
g–1 fibre, while Frieser reported that the acetic acid content of New
Zealand flax was 62.5 mg g–1 fibre [23]. Both of these data are con-
siderably greater than the level observed in the ageing experiment.
Similarly, the xylan content of P. tenax was recorded as 240 mg g–1
fibre [23] and since the furfural is derived largely from this fraction
of the fibre [7], the furfural produced in the ageing experiment after
55 days was only a small proportion (∼ 0.75%) of that which could
be produced potentially.
If the curve for the acetic acid graph given in Fig. 1 is extrapo-
lated, it suggests that the production of acetic acid from the sample
would reach the level of 19 mg g–1 fibre after 270 days (∼ 9 months)
ageing under the conditions described.
In this work, the production of acetic acid and furfural from
the hemicellulose of fibres of P. tenax during accelerated ageing
was examined by HS-SPME and GC–MS in order to estimate the
longevity of such fibres. Other published methods for determining
the durability (of paper) include changes in the degree of polymer-
ization of cellulose during accelerated ageing [36,37] and physical
changes over time of the tensile strength of various papers with
changes in humidity and temperature [38]. These methods were
used to determine the rates of change from the Arrhenius equa-
tion and then to predict the stability of various papers over time at
ambient temperatures. Such detailed analyses however are compli-
cated by variables such as the material (whether fibre or paper), its
chemical composition, pH, humidity, temperature, light, additives
and atmospheric contaminants, so that application of a general rate
equation to the degradation of fibrous materials is difficult. Never-
theless, Zou et al. [36] demonstrated that the rate of degradation
of paper was strongly dependent on pH as the degree of polymer-
ization (DP) of the cellulose of an acidic sample of paper decreased
from 760 to 250 in only 22 years of natural ageing at ambient tem-
peratures whereas the DP of a sample with an alkaline pH was
unchanged over the same period.
 R.J. Weston et al. / Journal of Cultural Heritage 13 (2012) 413–418
The fibre extracted from P. tenax that was used in the present
work was shown to produce acetic acid at increasing rates
over a relatively short period which, along with the work of
Zou et al. [36], suggests that that if a museum artefact, made
from P. tenax fibres, were to be stored in damp conditions,
then it could deteriorate significantly over a relatively short
period, due largely to the hydrolytic effect of acetic acid on the
fibres.
4.7. Conservation of cultural artefacts made from fibres of P. tenax
Many museum objects, made from cellulosic materials, pro-
duce acetic acid. This acid is generated from within fibrous objects
by the environment in which they are displayed and so “most
preservation work will be preventative in nature. It is better
to protect the records and control their environment than to
spend resources and time repairing damage” [39]. The results of
the work in this paper and work quoted within it, suggest that
control of humidity is the most important factor in a conser-
vation programme that is designed to minimize the production
of acetic acid. Secondary factors, appropriate to the preservation
of artefacts made from P. tenax and other plant fibres, include
the addition of containers of absorbent bases, such as magne-
sium carbonate or calcium carbonate or solid chemical buffers, or
scavengers such as activated carbon or zeolites, to display cabi-
nets, to absorb the acetic acid and any other volatile acids that
may emanate from the displayed or archived objects. For those
objects that are displayed in large spaces, continuous change
of the air or efficient filtered air-conditioning or air movement
are required to minimize the levels of acetic acid in such areas.
Although P. tenax fibres contain a high proportion of hemicellu-
lose (and acetate groups) compared with other plant fibres, all
plant fibres contain some hemicellulose and so artefacts, made
from these materials, should be stored or displayed under these
conditions.
5. Conclusions
SPME–GC–MS methodology has been applied to the analysis of
acetic acid and furfural that is generated during ageing of the fibres
of P. tenax (New Zealand flax).
Accelerated hydrothermal ageing of the fibres of P. tenax at
70 ◦ C for a period of 55 days produced acetic acid and furfural at
levels of approximately 1.65 mg g–1 fibre and 1.85 mg g–1 respec-
tively. These yields were only a small proportion of the potential
production of these chemicals from P. tenax fibre. However, if an
object that was made of fibres of P. tenax were to be stored under
damp conditions, then the amount of acetic acid produced could
cause significant damage to such an object after a relatively short
period.
Other observed chemical products of degradation of the fibres
were a series of short to medium chain aliphatic aldehydes that
were derived from the degradation of long chain fatty acids in the
leaf of the flax and a small group of nor-isoprenoids that were
derived from carotenoids in the leaf.
The fibres from six cultivars of P. tenax were subjected to acceler-
ated hydrothermal ageing and in all these cases, the fibre produced
acetic acid and furfural at approximately the same rate and in the
same yield.
Reduction of humidity coupled with continuous changes of air
in display or storage areas of a museum or archive are important
aspects of a program to conserve cultural objects made from plant
fibres by minimizing the production from and effects of acetic acid
on such objects.
417
Acknowledgement
This research was financially supported by the New Zealand
Ministry of Science and Innovation, contract VICX0501.
References
[1] G. Buchbauer, L. Jirovetz, M. Wasicky, A. Nikiforov, On the odour of old books,
J. Pulp Pap. Sci. 21 (1995) 398–400.
[2] A. Fenech, M. Strlič, I.K. Cigić, A. Levart, L.T. Gibson, G. de Bruin, K. Ntanos, J.
Kolar, M. Cassar, Volatile aldehydes in libraries and archives, Atmos. Environ.
44 (2010) 2067–2073.
[3] A.F.L. Godoi, L. Van Vaeck, R. Van Grieken, Use of solid-phase microextraction
for the detection of acetic acid by ion-trap gas chromatography-mass spec-
trometry and application to indoor levels in museums, J. Chromatogr. A. 1067
(2005) 331–336.
[4] M. Strlič, I.K. Cigić, J. Kolar, G. De Bruin, B. Pihlar, Non-destructive evaluation of
historical paper based on pH estimation from VOC emissions, Sensors 7 (2007)
3136–3145.
[5] M. Strlič, J. Thomas, T. Trafela, L. Cséfalvayová, I.K. Cigić, J. Kolar, M. Cassar, Mate-
rial degradomics: on the smell of old books, Anal. Chem. 81 (2009) 8617–8622.
[6] E.M. Gaspar, J.C. Santana, J.F. Lopes, M.B. Diniz, Volatile organic compounds in
paper – an approach for identification of markers in aged books, Anal. Bioanal.
Chem. 397 (2010) 369–380.
[7] A. Lattuati-Derieux, S. Bonnassies-Termies, B. Lavédrine, Characterisation of
compounds emitted during natural and artificial ageing of a book. Use of head-
space-solid-phase microextraction/gas chromatography/mass spectrometry, J.
Cult. Herit. 7 (2006) 123–133.
[8] A. Lattuati-Derieux, S. Bonnassies-Termies, B. Lavédrine, Identification of
volatile organic compounds emitted by a naturally aged book using solid-phase
microextraction/gas chromatography/mass spectrometry, J. Chromatogr. A
1026 (2004) 9–18.
[9] P.M. Wehi, B.D. Clarkson, Biological flora of New Zealand 10. Phormium tenax,
harakeke, New Zealand flax, New Zeal. J. Bot. 45 (2007) 521–544.
[10] E. Puketapu-Hetet, Maori Weaving, Pitman, Auckland, 1989.
[11] R. Te Kanawa, S. Thomsen, G. Smith, I. Miller, C. Andary, D. Cardon, Traditional
Maori dyes, Dyes Hist. Archaeol. 18 (2002) 47–50.
[12] N. Moore, G. Smith, R. Te Kanawa, I. Miller, Iron-sensitive degradation of black-
dyed Maori textiles, Dyes Hist. Archaeol. 19 (2003) 144–148.
[13] V. Daniels, Factors affecting the deterioration of the cellulosic fibres in black-
dyed New Zealand flax (Phormium tenax), Stud. Conserv. 44 (1999) 73–85.
[14] S. Scheele, G. Walls, Harakeke. The Rene Orchiston collection, Manaaki Whenua
Press, Lincoln, New Zealand, 1994.
[15] S.M. Scheele, R.D. Smissen, Insights into the origin and identity of national New
Zealand flax collection plants from simple sequence repeat (SSR) genotyping,
New Zeal. J. Bot. 48 (2010) 41–54.
[16] W. Harris, S.M. Scheele, G.J. Forrester, K. Te Kanawa, M. Murray, E. Pahewa, Vari-
etal differences and environmental effects on fibre extracted from Phormium
leaves and prepared for traditional Maori weaving, New Zeal. J. Bot. 46 (2008)
401–423.
[17] D.J. Carr, N.M. Cruthers, R.M. Laing, B.E. Niven, Fibers from three cultivars of
New Zealand flax (Phormium tenax), Text. Res. J. 75 (2005) 93–98.
[18] N.M. Cruthers, D.J. Carr, R.M. Laing, B.E. Niven, Structural differences among
fibers from six cultivars of Harakeke (Phormium tenax, New Zealand flax), Text.
Res. J. 76 (2006) 601–606.
[19] A.J. Turner, The structure of textile fibres. VIII. The long vegetable fibres, J. Text.
I 40 (1949) 972–982.
[20] H.L. Spiegelberg, The effect of hemicelluloses on the mechanical properties of
individual pulp fibers, Tappi. 49 (1966) 388–396.
[21] N. Cruthers, D. Carr, R. Laing, The New Zealand flax fibre industry, Text. Hist. 40
(2009) 103–111.
[22] M.A. Tariq, The xylan from New Zealand flax (Phormium tenax), PhD thesis,
University of Otago, 1994.
[23] E. Frieser, The quantitative determination of the noncellulosic constituents of
vegetable fibers, II, Textil-Rundschau 16 (1961) 304–314.
[24] R.H. Newman, S.E.K. Tauwhare, T.C. Davidson, S. Scheele, R. Te Kanawa,
Phormium (New Zealand flax) as a source of fibres for composite materials, in:
Proceedings of the 13th International symposium on wood, fibre and pulping
chemistry (ISWFP), Auckland, New Zealand, May, 2005.
[25] T. Łojewski, T. Sawoszczuk, J.M. Łagan, K. Zieba, ˛ A. Barański, J. Łojewska, Furfural
as a marker of cellulose degradation. A quantitative approach, Appl. Phys. A 100
(2010) 873–884.
[26] O. Ramalho, A.-L. Dupont, C. Egasse, A. Lattuati-Derieux, Emission rates of
volatile organic compounds from paper, Preserv. Sci 6 (2009) 53–59.
[27] K.J. Jardine, E.D. Sommer, S.R. Saleska, T.R. Huxman, P.C. Harley, L. Abrell, Gas
phase measurements of pyruvic acid and its volatile metabolites, Environ. Sci.
Technol. 44 (2010) 2454–2460.
[28] G. Spiteller, W. Kern, P. Spiteller, Investigation of aldehydic lipid peroxida-
tion products by gas chromatography-mass spectrometry, J. Chromatogr. A 843
(1999) 29–98.
[29] S.M. Kupchan, H. Meshulam, A.T. Sneden, New cucurbitacins from Phormium
tenax and Marah oreganus, Phytochemistry 17 (1978) 767–769.
[30] G.J. Smith, R. Chadwick, N. Konese, S. Scheele, S.E. Tauwhare, R.J. Weston,
Photodegradation of Phormium tenax fibres: the role of naturally occurring
418 R.J. Weston et al. / Journal of Cultural Heritage 13 (2012) 413–418
coumarins, AHRC research centre for textile conservation and textile studies,
3rd Annual Conference, July 11–13, Postprints, in: M. Hayward, E. Kramer (Eds.),
Textiles and text: re-establishing the links between archival and object-based
research, Archetype Publications, 2006.
[31] P. Kanasawud, J.C. Crouzet, Mechanism of formation of volatile compounds by
thermal degradation of carotenoids in aqueous medium. 1. ␤-carotene degra-
dation, J. Agr. Food Chem. 38 (1990) 237–243.
[32] S. Isoe, S. Katsumura, T. Sakan, The synthesis of damascenone and ␤-damascone
and the possible mechanism of their formation from carotenoids, Helv. Chim.
Acta 56 (1973) 1514–1516.
[33] G.K. Skouroumounis, R.A. Massy-Westropp, M.A. Sefton, P.J. Williams, Precur-
sors of damascenone in fruit juices, Tetrahedron Lett. 33 (1992) 3533–3536.
[34] M.M. Mendes-Pinto, Carotenoid breakdown products the nor-isoprenoids in
wine aroma, Arch. Biochem. Biophys. 483 (2009) 236–245.
[35] S.M. Benn, T.L. Peppard, Characterization of tequila flavour by instrumental and
sensory analysis, J. Agr. Food Chem. 44 (1996) 557–566.
[36] X. Zou, T. Uesaka, N. Gurnagul, Prediction of paper permanence by accelerated
aging II. Comparison of the predictions with natural aging results, Cellulose 3
(1996) 269–279.
[37] H.-Z. Ding, Z.D. Wang, Time-temperature superposition method for predicting
the permanence of paper by extrapolating accelerated ageing data to ambient
conditions, Cellulose 14 (2007) 171–181.
[38] B. Havlínová, S. Katuščák, M. Petrovičová, A. Maková, V. Brezová, A study of
mechanical properties of papers exposed to various methods of accelerated
aging. Part I. The effect of heat and humidity on original wood-pulp papers, J.
Cult. Herit. 10 (2009) 222–231.
[39] M. Roper, L. Millar (Eds.), Managing public sector records, a study programme,
International Records Management Trust, London, 1999, p. 33.