Journal of Cultural Heritage 12 (2011) 205–213

Original article

Indoor air quality in passive-type museum showcases

Alexandra Schieweck ∗ , Tunga Salthammer 1
Fraunhofer Wilhelm-Klauditz-Institute (WKI), Material Analysis and Indoor Chemistry, Bienroder Weg 54E, 38108 Braunschweig, Germany

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

Article history: Air pollution in museum showcases is one main problem within preventive conservation. Applied mate-
Received 11 August 2009 rials for construction and decoration of showcases are potential emission sources for a broad variety of
Accepted 21 September 2010 volatile organics. These might accumulate under those almost static conditions that are set within show-
Available online 16 December 2010
cases due to conservation requirements. In particular, the knowledge of the potential hazardous impact
of airborne pollutants on cultural assets caused a fundamental shift in material selection for showcase
Keywords: production during the last decades. However, systematic indoor air analyses within those modern-type
Museums
showcases are missing so far. Hence, there is no knowledge if there has been achieved any improve-
Showcases
Airborne pollutants
ment of air quality compared to traditional enclosures. In order to make the first move for evaluating
Air quality the current situation in museum showcases, air analyses within passive-type enclosures of different
VOCs construction types and ages have been performed. The focus was on concentrations of volatile and semi-
volatile organic compounds (VOCs/SVOCs). Formaldehyde and organic acids have also been considered
due to their known corrosive impact. All these target compounds have been determined by active and
passive sampling and subsequent chemical analysis. It was found that in contrast to old-type show-
cases main emission sources have shifted from wood-based products and acid curing silicone rubbers to
solvent-borne lacquers and neutral curing sealants. Due to secondary reactions, levels of acetic acid are
still elevated. Thus, damage on artefact materials can still be suspected. The results reveal that a careful
selection of construction materials is often not sufficient to lower air pollution levels. The development
of risk assessment strategies and new technologies is therefore recommended.
© 2010 Elsevier Masson SAS. All rights reserved.

1. Introduction showcases are constructed as airtight as possible at the request of

Showcases are today an integral part of museums’ furniture as
many museum institutions are using a so-called “box in a box-
model” [1] as an underlying strategy to preserve artefacts in an
optimum way. In order to achieve an all-embracing control of the
surrounding conditions and to minimize environmental influences
(climate fluctuation, entry of polluted outer air), climatic demands
within:
• the museum building;
• galleries, exhibition areas and storage rooms;
• showcases;
are closely defined.
Showcases are therefore both to protect the items on dis-
play against undesired environmental influences and mechanical
impact. In order to meet these requirements, the vast majority of
∗ Corresponding author. Tel.: +49 531 2155 924; fax: +49 531 2155 905.
E-mail addresses: alexandra.schieweck@wki.fraunhofer.de (A. Schieweck),
tunga.salthammer@wki.fraunhofer.de (T. Salthammer).
1
Tel.: +49 531 2155 350; fax: +49 531 2155 905.
conservators and exhibition technicians as the microclimate inside
seems to be more controllable than within non-airtight enclosures,
e.g. in regards to the entry of dust, pollutants, climatic fluctuations
or pests. Some showcases might also be equipped with technical
devices, i.e. for active air ventilation, positive pressure or with inert
gas. However, due to financial reasons most showcases are pas-
sive systems with no active air ventilation and/or filtration. The
resulting almost static conditions combined with a variety of con-
struction and decoration materials favours the accumulation of
chemical emissions inside. Moreover, particularly smaller show-
cases are characterized by a high surface-to-volume ratio. These
parameters set the museum situation apart from normal indoor
scenarios. Hence, the comparison of the indoor environment as a
“reaction vessel”, as stated by Weschler and Shields [2], comes to a
head in museum showcases.
The fact that materials applied for showcase production might
contribute to a bad air quality or even cause damage on arte-
facts was early observed and attracted the attention in the last
decades [3–5]. Accordingly, main research focussed on formalde-
hyde, formic acid and acetic acid as degradation effects appear
quickly at exposure to these volatiles [6–9]. Corresponding reaction
mechanisms were therefore utilized for developing accelerated
corrosion tests to check the suitability of materials for applica-

1296-2074/$ – see front matter © 2010 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.culher.2010.09.005
206 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213
tion in the museum environment in a simple and inexpensive
way without the need of sophisticated laboratory facilities [10–13].
Consequently, specific materials for showcase production known
for emitting hazardous compounds, such as wood-based products
and acid curing silicone sealants, were increasingly substituted by
so called inert materials and products which are assumed to be
low-emissive. Nevertheless, complaints are still expressed by con-
servators. Special problems seem to be significant odorous loads,
high pollution levels and unspecific signs of damages.
1.1. Research aims
Even though the protection performance of showcases was
discussed by Camuffo et al. [1] and first insights into the air pol-
lution problem were given by some previous studies [14–17],
fundamental investigations on air quality within museum enclo-
sures are missing so far. Furthermore, volatile and semi-volatile
organic compounds (VOCs/SVOCs) have not been considered until
now, although it was reported that they are significantly influenc-
ing indoor air quality with a potential impact on cultural assets
and human health [18] as demonstrated in some previous studies
[19,20].
A two-year research project targeted therefore to create a com-
prehensive picture of the current situation of air quality in museum
enclosures. The study has been realised in close cooperation with
showcase manufacturers with a special focus on passive-type
showcases. In a first step, a broad range of materials that are cur-
rently widely used for showcase production were subjected to
material emission analyses. In order to obtain an exact identi-
fication and quantification of released substances, sophisticated
material emission tests were used [21]. The results are reported
elsewhere [22,23]. Subsequently, air analyses within showcases of
different construction types (airtight vs. open) and ages (days vs.
years) have been performed. These comparative tests targeted on
revealing differences and/or correlations between the spectrum of
emitted substances and the range of pollution levels, also over long
term. In addition, it should be answered if any improvement has
been achieved by the shift in material selection. Influencing fac-
tors, such as air exchange rates, artificial lighting and emissions
from artefact materials themselves [24] have additionally been con-
sidered. Emphasize was on VOCs and SVOCs as this is the major
category among indoor air pollutants. Formaldehyde, formic acid
and acetic acid have also been included due their known corro-
sive impact. According to findings from indoor chemistry, it was
furthermore of interest if secondary reactions [25] proceed within
showcases.
2. Experimental
2.1. Showcase selection and preparation
During this study, two main showcase construction types were
distinguished (a) modern-type showcases and (b) old-type show-
cases. Modern-type enclosures are predominantly built from e.g.
glass, powder coated or lacquered metals, neutral curing silicone
Table 1
Investigated showcase types, their kind of use, ages and applied construction materials.
Showcase type Kind of use Age
Modern-type (N) Directly after production 1–28 days
Modern-type (M) In museum use 2–4 years
Old-type (O) In museum use Several decades
N = number of investigated showcases.
rubber and just rarely wood-based products. They have been exam-
ined both directly after production at the manufacturers site (N)
and after different time in museum use (M). Old-type showcases
(O) are of traditional style and predominantly constructed by wood-
based products, felt and acid curing silicone sealants. Those types
were mostly constructed before the 1990s. Regarding showcases
in museums, no detailed information was available about specific
construction and decoration materials due to different reasons.
Some enclosures were several years old and no documentation
about the purchase was on hand, for other showcases, no mate-
rial information was provided by the manufacturers. Therefore,
Table 1 gives a brief overview of the tested showcase types by pro-
viding general information about the kind of use, construction types
and applied building products. In contrast, technical data regard-
ing modern-type showcases that were tested immediately after
production (N) were made available by the manufacturers and are
listed in Table 2.
The showcases were closed at least one week before start of
investigation in order to reach equilibrium of material emissions
and air concentration. During sampling it was not allowed to open
the enclosure. Air was sucked through small tubes, which were
brought in from outside, where they were coupled with the sam-
pling devices. During measurements, showcases had no technical
equipment, e.g. buffer materials or lighting. Parallel to showcase
analyses, air sampling was performed in the environmental room to
reveal possible diffusion processes between the indoor air and the
showcases air and, thus, for clear identification of emission sources.
2.2. Sampling and analysis
2.2.1. Volatile organic compounds
Active air sampling of volatile organic compounds (VOCs)
(150 ml min−1 , 40 min) was done with stainless steel desorp-
tion tubes (Perkin Elmer) filled with Tenax TA® (60/80 mesh,
Chrompack). Multibed sorbent tubes packed with Tenax TA® and
CarboTrap® (20/40 mesh, Chrompack) were utilized for sampling
volatile monoterpenes [26]. Passive air sampling was performed if
showcase volumes were too small, especially regarding table dis-
play cases, or if no outer access was available. Tenax TA® -tubes
were hung with one closed end and one end equipped with a diffu-
sion cap in the showcase for 14 days. After exposure, the tubes were
thermally desorbed (320 ◦ C, 10 min; Perkin Elmer ATD 400) into a
GC/MS system (Agilent 6890/5972). The compounds were sepa-
rated on a HP-5 MS column (60 m × 0.25 mm, 0.25 ␮m). Qualifying
was based on a PBM library search [27]. Moreover, mass spectra and
retention data were compared with those of reference compounds.
Regarding active air sampling, all identified compounds were quan-
tified using their own response factors. The areas of unidentified
peaks were converted to concentrations using the toluene response
factor. For calibration a linear regression model was used [28].
Results obtained by passive sampling were calculated using dif-
fusive uptake rates [29] and substance-specific conversion factors.
N Short description of construction type
7 Freestanding showcases, highly sealed, glass cubes with glass cover
plates, lacquered fibreboard base plates, no technical equipment
11 Freestanding showcases, highly sealed, glass cubes, lacquered wooden
base plates, lacquered metal/wooden cover plates
14 Freestanding or wall showcases, glass cubes, lacquered wood-based
materials (base and cover plates, back boards), partially felt
 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213 207

2.2.2. Formaldehyde, formic acid and acetic acid

Sampling of formaldehyde (HCHO) was performed by passing

Polybutadiene rubber UV-curing

80 L of air with a flow of 2 L min−1 through a liquid absorber

Alkoxy curing silicone rubber

Alkoxy curing silicone rubber

Alkoxy curing silicone rubber

(distilled water). For analysis, formaldehyde was derivatized to

Two-pack methacrylate
3,5-diacetyl-dihydrolutidine (DDL) with 2,4-pentanedione and
ammonium acetate. DDL was then measured fluorimetrically at a

UV-curing adhesive
wavelength of  = 510 nm [30].
Gasket materials

Formic acid (HCOOH) and acetic acid (CH3 COOH) were absorbed
in 0.1 n NaOH (120 L of air with a flow of 2 L min−1 ). High Per-
adhesive

formance Ion Chromatography Exclusion (HPICE) was applied for

analysis (Metrosep Organic Acids, 250 mm, Methrom) [31]. For cal-
–

–
ibration a linear regression model was used [32].

two-pack polyurethane
Two-pack polyacrylate

coating/solvent-borne

coating/solvent-borne

polyacrylate (topcoat)
2.2.3. Measurement of air exchange rates

Two-pack synthetic
For measuring air exchange rates within showcases the
Polyvinyl butyral
Coating systems

resin (primer)
Glass coating:
concentration-decay method was utilized [33]. The measuring
device and a fan were mounted inside the enclosure. After closing,
(topcoat)
(primer)

lacquera

lacquera
Powder

Powder

the showcase was doped with tracer gas (∼200 ppm N2 O) through
a tiny hole in the cover plate. The fan inside ensured a homoge-
–

nous mixing of the tracer gas with the air. The decreasing tracer
gas concentration was plotted against time with a N2 O-analyser
Cover plate

(Leybold-Heraeus BINOS) and was also recorded with a voltmeter

(Metex M-3610D). According to VDI 4300-7 [33], the decay in tracer
Glass

Glass

Glass
MDF

gas concentration for ideal mixing of the tracer gas with the room
–

air is given by equation (1):

Backboard

t = t=t0 · e−nt (1)

Glass

Glass

Glass
MDF

Two measured values give the air exchange rate n according to

–

equation (2):
1 t=t1
n= · ln
Chipboard with laminated

(2)
t2 − t1 t=t2
Overview of construction materials applied in modern-type showcases investigated immediately after production (N).

with n = air exchange rate [h−1 ], t = time of sampling the tracer gas
[h], t=t0 = initial tracer gas content [cm3 of tracer gas/m3 of tracer
gas air mixture] at time t = t0 (start of injection), t=t1 = tracer gas
cut surfaces

content [cm3 of tracer gas/m3 of tracer gas air mixture] at time t = t1

[h] and t=t2 = tracer gas content [cm3 of tracer gas/m3 of tracer gas
Shelf

MDF

MDF

MDF

air mixture] at time t = t2 [h].

–

Due to the expected low air exchange rates, measurements were

Showcase type

accomplished at least over 15 h. It is important to perform measure-

Freestanding

Freestanding

Freestanding

Freestanding

ments without buffer materials (e.g. silica gel), which are mostly
integrated in the base plate to compensate climatic fluctuations, as
they absorb tracer gases utilized for air exchange analyses (Fig. 1).
–

–
Volume (m3 )

0.68

0.68

0.76

0.68

0.83

0.83
–
Age (days)

1–21
28
1

7
Showcase N1.1

Showcase N1.2

Showcase N2.1

Showcase N2.2

Showcase N2.3
Showcase N3.1

Showcase N3.2

No more details available.

Location

–: no information available.
Manufacturer
Table 2

Fig. 1. N2 O-decrease over time in a 1 m3 glass test chamber without silica gel and
1

with 1200 g silica gel.

208 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213

As the measuring device has to be positioned inside the show-
case, air exchange rates could not be determined for showcases
in museum use with items on display. Air exchange rate measure-
ments were also not accomplished in the surrounding exhibition
rooms.
3. Results and discussion
Tables 3–5 give overviews of main results from the three inves-
tigated showcase types (N, M, O) by summarizing the particular
showcases age, the volume, the climatic parameters as well as
sum values of detected VOCs [ (VOC)], formaldehyde (HCHO),
formic acid (HCOOH) and acetic acid (CH3 COOH). Moreover, air
exchange rates (n) are compiled. Comparison measurements con-
ducted in exhibition rooms and production halls, respectively, are
given below the related showcase(s).
3.1. Modern-type showcases directly after production (N)
Analyses were performed while the showcases were positioned
in the production halls of the manufacturers. Climatic conditions
in the halls were comparable
with those inside museum exhibition
rooms (∼23 ◦ C, ∼50% RH). (VOC)-values within showcases var-
ied from 3819 up to 25,213 ␮g m−3 at volumes between 0.68 and
0.83 m3 (Table 3). Concentrations within showcases were higher
than elevated background values in the production halls. As in the
halls windows and doors were always open, air exchange rates can
be assumed to be greater than 1 h−1 . In contrast, air exchange rates
within showcases varied between 0.01 and 0.05 h−1 .
Within examined showcases, between 26 and 45 individ-
ual substances were identified and could be clearly attributed
to specific emission sources. Table 6 gives an overview about
most abundant volatile organics, their CAS registry number and
the emission source to which they are attributed. Aromatic
hydrocarbons, (di)carboxylic esters and glycol esters as well as
n-/iso-alkanes and ketones were detected within all enclosures.
These solvents and additives were released as primary emissions
mainly fromsolvent-borne coating systems, which contributed
30–50% to (VOC)-values. The second main emission sources
were identified as silicone rubber sealants splitting
 off elevated
concentrations of cyclic siloxanes (∼25% of (VOC)-values). In
showcase N1.2 (manufacturer 1) and showcase N2.1 (manufac-
turer 2), siloxane values were greater than 3000 ␮g m−3 . During
the curing process of one-pack room-temperature vulcanizing
systems (RTV-1), ketoximes as fragmentation products of cross-
linking agents are formed and released [23,34]. These substances
were therefore analysed in increased concentrations in showcase
N2.2 (17,709 ␮g m−3 ). Characteristic fragmentation compounds are

Table 3
Main results of indoor air analyses in newly (N) constructed showcases. Results of environmental room analyses are given below.

Manufacturer Location Age (days) Volume (m3 ) T (◦ C) RH (%) Active/passive (VOC) HCHO HCOOH CH3 COOH n (h-1 )
sampling (␮g m−3 ) (␮g m−3 ) (␮g m−3 ) (␮g m−3 )

1 Showcase N1.1 1 0.68 – – Active 7071 33 33 2294 0.02

Showcase N1.2 1 0.68 – – Active 5125 27 30 2209 –
Production hall – – 23 49 Active 1579 15 38 1414 –
2 Showcase N2.1 7 0.76 – – Active 9328 68 80 2352 –
Production hall – – – – Active 4014 20 n.d. 405 –
Showcase N2.2 28 0.68 – – Active 25,213 – – – –
Showcase N2.3 1–21 – – – Active 4378 – n.d. n.d. 0.05
Production hall – – 20 48 Active – – – – –
3 Showcase N3.1 7 0.83 – – Active – – n.d. 456 0.01
Showcase N3.2 7 0.83 – – Active 3819 35 n.d. 397 –
Production hall – – 23 55 Active 1882 24 n.d. 289 –

–: not determined; n.d.: not detected.

Table 4
Main results of indoor air analyses in modern-type (M) showcases in museum use. Results of environmental room analyses are given below.

Museum Location Age Volume (m3 ) T (◦ C) RH (%) Active/passive (VOC) (␮g m−3 ) HCHO HCOOH CH3 COOH n (h-1 )
sampling (␮g m−3 ) (␮g m−3 ) (␮g m−3 )

1 Showcase M1.1 ∼5 yrs – – – Passive 2192 – – – –

Exhibition room – – 20 55 Active 469 16 45 339 –
4 Showcase M4.1a ∼3 months – – – Active 3055 29 348 262 –
Exhibition room – – 19 42 Active 240 12 261 316 –
5 Showcase M5.1 ∼4 months 0.68 – – Active 1907 52 89 831 –
Showcase M5.2 ∼4 months 0.68 22 45 Active 1203 41 95 876 0.04
Exhibition room – – 21 42 Active 290 20 42 212 –
6 Showcase M6.1a,c ∼1–2 yrs – – – Active 682 17 n.d. 133 –
Exhibition room – – 18 50 Active 528 22 n.d. n.d. 4
7 Showcase M7.1b,c ∼2 yrs 1.45 – – Active 868 24 n.d. 108 –
Exhibition room – – 18 46 Active 887 17 n.d. 249 –
Showcase M7.2b ∼4 yrs 0.68 – – Active 26,516 28 n.d. 461 0.01
Showcase M7.3b ∼4 yrs 0.71 23 54 Active 16,830 46 n.d. 508 –
Production hall – – 20 57 Active 7349 39 n.d. 354 –
8 Showcase M8.1a,c ∼9 yrs 0.58 – – Active 102 n.d. n.d. n.d. –
Exhibition room (vault) – – 19 48 Active 67 n.d. n.d. n.d. –
Showcase M8.2a ∼3 yrs 0.97 – – Active 1358 158 350 4935 –
Exhibition room – – 23 29 Active 83 14 46 111 –
Showcase M8.3a ∼6 yrs 1.1 – – Active 16,098 147 348 5698 –
Special exhibition room – – 22 45 Active 200 54 95 436 –

–: not determined; n.d.: not detected.

a
With items on display.
b
At the manufacturer.
c
Open construction type.
 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213 209

Table 5
Main results of indoor air analyses in old-type (O) showcases in museum use. Results of environmental room analyses are given below. Air exchange rate measurements
could not be performed as items were on display.

Museum Location Age Volume (m3 ) T (◦ C) RH (%) Active/passive (VOC) HCHO HCOOH CH3 COOH
sampling (␮g m−3 ) (␮g m−3 ) (␮g m−3 ) (␮g m−3 )

1 Diorama O1.1a 12 22 45 Active 758 69 106 452

Exhibition room – – 23 41 Active 745 45 87 298
Diorama O1.2a 12 22 45 Active 745 – – –
Exhibition room – – 22 41 Active 712 – – –
Diorama O1.3a 12 – – Passive 362 – – –
Showcase O1.4a – – – Passive 215 – – –
Showcase O1.5a – – – Passive 522 – – –
Exhibition room – – 21 46 Active 319 18 111 306
Showcase O1.6a 0.5 – – Passive 133 – – –
Exhibition room – – 20 47 Active 347 18 102 393
Showcase O1.7a 2 – – Passive 2800 – – –
Exhibition room – – 20 55 Active 469 16 45 339
Showcase O1.8a ∼20 yrs 4.8 23 58 Active 2101 757 656 3282
Passive 1057 – – –
Showcase O1.9a 0.68 – – Active 1859 435 405 1157
Exhibition room – – 22 34 Active 520 47 170 526
2 Showcase O2.1a,b ∼20 yrs – 25 46 Active 87 91 218 527
Exhibition room – – 24 50 Active 86 46 105 345
Storage case O2.2a ∼20 yrs – – – Active 659 322 364 1490
Exhibition room – – 24 49 Active 79 56 112 332
3 Showcase O3.1a ∼20 yrs – – – Active 239 326 710 2598
Exhibition room – – 26 43 Active 135 17 58 416
Showcase O3.2a ∼20 yrs 0.5 – – Active 102 310 782 2101
Exhibition room – – 25 41 Active 193 21 64 450

–: not determined; n.d.: not detected.

a
With items on display.
b
Open construction type.

Table 6
Main characteristic compounds that were identified in the majority of investigated modern-type and old-type showcases by GC/MS.

Substance CAS-No. Modern-type/old-type showcases Emission sources

Alcohols
Ethanol 64-17-5 +/− Coating materials, sealants
n-Propanol 71-23-8 +/+ Coating materials, sealants
n-Butanol 71-36-3 +/− Coating materials, sealants
Aldehydes
Hexanal 66-25-1 −/+ Wood-based materials, degradation product
Nonanal 124-19-6 −/+ Wood-based materials, degradation product
Furfural 98-01-1 −/+ Wood-based materials, degradation product
Monoterpenes
␣-Pinene 80-56-8 −/+ Wood-based materials
␤-Pinene 127-91-3 −/+ Wood-based materials
Limonene 138-86-3 −/+ Wood-based materials
3-Carene 13466-78-9 −/+ Wood-based materials
Aromatic hydrocarbons
Toluene 108-88-3 +/+ Coating materials, sealants
Ethyltoluenesa – +/− Coating materials, sealants
m,p-Xylene 1330-20-7 +/+ Coating materials, sealants
o-Xylene 95-47-6 +/+ Coating materials, sealants
Ethylbenzene 100-41-4 +/− Coating materials, sealants
Trimethylbenzenesa – +/− Coating materials, sealants
Carboxylic acids
Acetic acid 64-19-7 +/+ Coating materials, wood-based products, degradation product
Carboxylic esters
Ethylacetate 141-78-6 +/+ Coating materials, sealants
n-Butylacetate 123-86-4 +/+ Coating materials, sealants
Glycol ethers
2-Butoxyethanol 111-76-2 +/+ Coating materials
1-Butoxy-2-propanol 5131-66-8 +/− Coating materials
Cyclic siloxanes – +/+ Silicone rubber sealants
Ketoximes
2-Butanone oxime (MEKO) 96-29-7 +/− Neutral curing silicone rubber sealants
4-Methyl-2-pentanone oxime (MIBKO) 105-44-2 +/− Neutral curing silicone rubber sealants
Glycol esters
Ethoxypropylacetate 98516-30-4 +/− Coating materials
Ethyl-3-ethoxypropionate 763-69-9 +/− Coating materials
1-Methoxy-2-propylacetate 108-65-6 +/+ Coating materials
a
Isomers not listed.
210 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213
2-butanone oxime (MEKO: methyl ethyl ketoxime) and 4-methyl-
2-pentanone oxime (MIBKO: methyl isobutyl ketoxime). Further
dominant substance groups were alcohols and cycloalkanes, which
were evaporated as solvent residues from lacquer systems and
sealants.
Concentrations
 of formaldehyde and formic acid were lower
than (VOC)-values within all showcases (27–68 and 30–80 ␮g
m−3 , respectively). Both substances might be attributed to wood-
based products, which have been installed as base plates. However,
levels of acetic acid were increased. In three enclosures (Table 3)
acetic acid values ranged between 2209 and 2352 ␮g m−3 . As in
most of the tested showcases just the base plates have been made
of wood-based products and facing the preceding material emis-
sion analyses [23,24], it is improbable that these heightened levels
exclusively result from wood-based materials, even though acetic
acid is one of their characteristic emissions. In contrast, all con-
structional elements within investigated showcases were coated
with solvent-borne lacquers (Table 2), whose main primary emis-
sions are (di)carboxylic esters and glycol esters. In accordance with
results obtained by material emission tests [23], acetic acid can
be generated within modern-type showcases as secondary emis-
sion product by hydrolytic cleavage of acetyl esters, as shown in
equation (3).
R 1 C(O)OR 2 + H2 O → R 1 COOH + R 2 OH
The deleterious effects of organic acids, especially acetic acid,
have been discussed thoroughly in the conservation commu-
nity and should not be repeated here. It is therefore referred
to the extensive literature [3,6,8,9,15,35]. Furthermore, Donovan
and Moynehan [36] reported that acidic emissions of air-drying
paints are able to corrode bare metals in the presence of moisture.
Organic vapours emitted by drying-oil paints, solvent acrylic and
nitrocellulose paint have been found to be corrosive. In a recent
publication, Schieweck and Salthammer [23] demonstrated that
also epoxy resin, cellulose nitrate, polyurethane and polyacrylate
lacquers release acetic acid mostly due to ester hydrolysis. It was
also reported that esters can solubilise coatings of paint media,
varnishes and resinous materials found associated with artefacts
[18].
3.2. Modern-type showcases in museum use (M)
Investigated modern type showcases were in museum use for
3 months up to 9 years. Showcases located in museum 7 (Table 4)
had been stored in the manufacturer exhibition since production
for 2 to 4 years, but were located as an exception in the production
halls at date of measurement.
All showcases were highly sealed to minimize outdoor influ-
ences but showcases M6.1, M7.1 and M8.1 (Table 4). Showcase M6.1
in museum 6 was consciously constructed with gaps between the
vertical glass edges of ca. 3 mm width to provide a continuously
air exchange. Glass edges of showcase M7.1 were not sealed in
the pedestal zone and therefore open to air movement, whereas
showcase M8.1 had wide gaps both in the base and in the cover
plate. Facing the results it becomes obvious that  pollution levels
are mainly influenced by the kind of construction. (VOC)-values
for sealed showcases ranged between 1203 and 26,516 ␮g m−3 ,
whereas (VOC)-values of open constructed showcases varied
from 102 to 868 ␮g m−3 .
Most abundant compounds (Table 6) corresponded inevitably
to those analyzed in modern-type showcases directly after produc-
tion (N), as the same materials were applied for construction and
decoration because they were mainly from the same manufactur-
ers. In the majority of highly sealed showcases (five out of eight)
between 45 and 47 individual substances were detected by active
air sampling compared with 10 up to 37 individual compounds in

open constructed types. Elevated (VOC)-values were analyzed
in showcases M7.2 and M7.3 at the manufacturers site, as summa-
rized in Table 4. The fact that these were located in a production
hall during measurements explains the heightened background

(VOC)-value of 7349 ␮g m−3 . As discussed above, this circum-
stance may inevitably contribute to some extend to increased
pollution levels because showcases might be opened. However, all
substances were detected several factors higher than in the produc-
tion hall so that accumulation of indoor generated emissions can be
suspected. Facing dominating substances, solvent-based lacquers
and silicone sealants
 were again the main emission sources.
Increased (VOC)-concentrations were also analyzed in show-
case M8.3 (16,098 ␮g m−3 ). During measurements, two Egyptian
mummies (items on loan) were exhibited inside the enclosure on
the occasion of a special exhibition. It was not possible to clearly
trace emissions from products for conservation and/or restoration
purposes. In principle, emissions of the mummies themselves can-
not be excluded. Due to the high concentrations, it is presumable
that artefact emissions were overlain. Furthermore, it is probable
that the showcase was redecorated over the years by the museum
staff itself. This could be a reason for the high air pollution levels
although the showcase was constructed 6 years ago.
Regarding open constructed enclosures, equilibrium will be
formed with the environmental room. Pollution levels in those con-
(3)
struction types are particularly low, if they are located in rooms
with minor background values, as showcase M8.1 (102 ␮g m−3 ),
which is located in the cellar vault of museum 8 (Table 4). Also
the exhibition roomin museum 6 proved to have a very low
background value ( (VOC): 528 ␮g m−3 ) as the setting of the
HVAC (heating ventilation air conditioning) system ensures an air
exchange rate (n) greater than 4 h−1 .
In general, values of formaldehyde and formic acid were in a
lower range, again particularly in showcases of open construction
types. Formic acid and acetic acid concentrations were elevated in
showcase M4.1 as in this enclosure wooden base plates have been
installed causing a high surface-to-volume ratio. Further excep-
tions were showcases M8.2 and M8.3. Showcase M8.2 exhibits an
archaeological wooden object, which is quite sensitive against fluc-
tuations in relative humidity. Thus, the showcase is equipped with a
pump for active air circulation and with a buffer material to ensure
a constant and homogeneous relative humidity of 50–55%. Specific
emission sources causing increased concentrations of formalde-
hyde, formic acid and acetic acid (Table 4) could not be clarified,
as there was no information available about applied construction
materials. As the showcase is in museum use since three years
and as it is mainly constructed from lacquered metals and glass,
elevated acetic acid concentrations were not expected. However,
facing the level of relative humidity it is supposed that either acetic
acid is formed as secondary emission by ester hydrolysis or due
to applied acid curing silicone rubbers. In addition it cannot be
excluded that the wooden artefact itself acts as emission source.
3.3. Old-type showcases in museum use (O)

(VOC)-concentrations obtained by active air sampling in
sealed old-type showcases ranged from 87 to 2101 ␮g m−3
(Table 5). Between 4 and 35 individual substances were identified,
as compiled in Table 6. High pollution concentrations detected in
showcase O1.8 (museum 1) were primarily caused by carboxylic
esters, especially acetic acid, constituting 67% of the (VOC)-value.
Showcase O2.1 and storage case O2.2 formed together one show-
case compartment. The showcase part was constructed with gaps
(∼4 mm width) so that air quality was nearly equal with the envi-
ronmental room. In contrast, (VOC)-values of the sealed storage
case were a factor of eight higher. As it was built from lacquered
fibreboard, characteristic emissions from wooden products and
 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213 211

Fig. 2. Comparison of substance group levels obtained by active and passive air sampling on Tenax TA® within showcase O1.8 (museum 1) (Table 4).

also typical solvent residues and additives were identified. The diffraction (XRD)2 . As the thermometer has been on display in this
same dominant substance groups were analysed within the dio- enclosure more than 20 years, it can be assumed that the corro-
rama. These are large enclosures illustrating landscapes by utilizing sion products have been formed due to exposure to acetic acid. As
a variety of products. Monoterpenes were identified in all show- reported by Grzywacz and Tennent [15], both compounds are often
cases whose occurrence is a significant evidence of the application found together on the same artefact.
of coniferous wood used for construction and furnishing show-
cases, such as pine and spruce [37].
Levels of formaldehyde and formic acid were increased and
ranged between 69 and 782 ␮g m−3 . Formic acid may be released
3.3.1. Passive versus active air sampling
from a primary emission source or may be formed by oxidation
As passive sampling seems more convenient and independently
of formaldehyde. In this case, formaldehyde would be the precur-
to perform without the need of laboratory staff on site, it is often
sor, but not the corrosive agent [38]. Thus, not the concentration
applied in museums by means of commercial available diffusion
of formaldehyde in the indoor atmosphere would be of impor-
tubes. As the principle of diffusive passive sampling is based on
tance, but the probability of oxidation to formic acid. Consequently,
gradient-driven diffusion, the application is characterized by long
formaldehyde would be just of hazardous potential for artefact
sampling times [26,40]. Exposition time should last for at least sev-
materials at very high relative humidities and at the unusual pres-
eral days or weeks in order to allow the gaseous volatiles to diffuse
ence of oxidants. Facing typical relative humidity levels in the
into the sampler and to be adsorbed inside [26]. As uptake rates
museum environment (50–55%) the impact of formaldehyde on
are influenced by the air-flow rate, this strategy is not convenient
artefact materials due to oxidation seems to be low. For a first
for low volumes and nearly static conditions which entail starva-
evaluation of the potential of formaldehyde to be oxidized, mea-
tion effects [40]. Moreover, the hindered penetration may cause an
surements of oxidizing agents are necessitated [38]. In addition to
underestimation of VOC concentration in comparison with active
adverse effects of formaldehyde due to oxidation to formic acid
sampling methods. Also the risk that VVOCs may not be trapped
and related corrosion effects (especially on metals and calcareous
on the sorbent sufficiently due to low interactions [26] contributes
materials), formaldehyde may also alter the characteristics of cel-
to lower results. Such reverse diffusion is especially encouraged by
lulosic materials such as paper and textiles regarding the pH-value
weaker adsorbents [40].
and the colour [39]. Proteins might denature and become brittle
Diffusive passive air sampling was performed in seven show-
and inelastic [39].
cases, as listed in Tables 4 and 5. 11–35% of the identified substances
Concentrations of acetic acid were elevated reaching up to
could not be quantified properly as no uptake rates are listed so
3282 ␮g m−3 . Showcase O1.8 in museum 1 exhibits the coat of a
far [29] and were, therefore, estimated on the basis of molecu-
bog body. In order to protect this light sensible object, the showcase
lar weights and structures. Hence, results are uncertain. In direct
has just a front glazing; the side walls and the backboard are light-
comparison of active and passive air sampling (Fig. 2), which
tight and consist of wood-based products covered with felt. These
has been performed in showcase O1.8, it becomes obvious that
materials caused high concentrations of formaldehyde, formic acid
some volatiles have not been trapped on the adsorbent, but were
and acetic acid (Table 5). Also the application of acid curing silicone
detectable by using active air sampling. Diffusive passive sampling
rubber as common in previous times cannot be excluded.
is therefore not the preferred method within museum showcases
In showcases O3.1 and O3.2 sensible metal instruments are
as air velocities are too low due to the almost static conditions.
exhibited. As listed in Table 5, values of formaldehyde, formic
acid and acetic acid are very high. White efflorescence on lead
bars from an antique thermometer, observed during a restoration
treatment, was identified as lead formate and basic lead carbon-
ate by Fourier transform infrared spectroscopy (FTIR) and X-ray 2
Herm, Ch. Dresden Academy of Fine Arts. Personal communication, 2005.
212 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213
4. Conclusions
During this study, a wide variety of showcases of different
construction types and ages has been investigated with a spe-
cial focus on VOCs and SVOCs. It was demonstrated that so called
old-type showcases, which had been constructed from traditional
materials, are characterized by a rather low number of differ-
ent VOCs, but heightened levels of formaldehyde, formic acid and
acetic acid. Examination results from eighteen modern-type show-
cases have shown that they are characterised by a broader range
of VOCs and still increased acetic acid concentrations despite of
another material choice. The differences in the span of individual
VOCs result from the fact that within investigated new-type show-
cases a wide spectrum of solvents and additives are released into
the gas phase. Most abundant compounds correspond with those
emissions known from building products for normal indoor use
[25,41–43]. This is not surprising as there are no special raw materi-
als available on the market, which have been especially designed for
museum purposes. Moreover, hydrolytic cleavage of acetyl esters
explains the still elevated acetic acid concentrations within mod-
ern museum showcases, even though no acidic formulations were
applied.
It was also found that air pollution levels within modern-type
showcases are markedly higher than those of traditional style.
Resulting from the airtight construction, organic volatiles accu-
mulate within modern-type showcases due to low air exchange
rates ranging around 0.01 h−1 . Lower pollutant concentrations
are attributed to an open construction provided that background
values in the surrounding room are low. However, non-airtight
enclosures are not as much favoured by conservators due to the
concern that dust, outdoor and indoor air pollutants are infiltrated
and security is lowered.
It has to be stressed that results are always depending on the
showcase construction type (e.g. passive vs. active; highly sealed vs.
open), technical and climatic parameters, the materials installed,
the item on display and the kind of use. Particularly emissions from
the exhibits themselves might be difficult to trace [24]. Also reno-
vations carried out by the museum staff will have a strong impact
on air pollution levels.
On the basis of the data it is obvious that findings from indoor
environments under residential or office use cannot be transferred
readily to the museum field. The statement that generally low-
emitting materials will give low-emitting structures [43] seems
not to be valid on the museum sector. It was found in this study
that pollution levels within passive-type showcases are increased.
Within preventive conservative strategies, prolonged ventilation
times before use of the showcase are recommended. However,
in everyday life time-schedules before exhibition openings are
often too tight to realise this approach. Hence, pollutant con-
centrations within sealed showcases will decrease, if at all, over
very long time periods. In conservation literature, coatings are
advised for sealing wooden panels. Concerning this matter, basic
research had been carried out by Miles [4] and Tétreault [44].
Although some coating formulations seem to be applicable for
blocking emissions from wooden products, liquid coating systems
emit in general characteristic volatiles and contribute therefore
to air pollution. Furthermore, it has to be considered that formu-
lations are frequently modified by industry without the need of
declaration [23]. Thus, it falls short of just recommending general
coating systems without performing periodical material emission
tests of considered paints. In some cases, composite materials (e.g.
polyethylene/aluminium/polyethylene films), so called vapour bar-
rier films, are sealed on wood-based products in order to reduce
their characteristic emissions. To be successful, the application has
to be performed careful to avoid open surfaces of the substrate or
the glue exposed to the air [18]. Nevertheless, it is recommended
just to select appropriate materials in order to prevent extensive
renovation work.
A first step in reducing airborne pollutants is the exclusion of
high emitting materials such as solvent-borne coatings and wood-
based products to keep emissions within museum enclosures as
low as reasonably achievable (ALARA). This ALARA approach is
generally accepted for indoor environments. In contrast to them,
there are no binding guideline values for museum interiors and
showcases so far. Tétreault [45] made a first approach by adopting
an evaluation scheme from toxicology. The obtained data depend
strongly on the specific experimental set-up. However, boundary
conditions within museum enclosures are too manifold (e.g. micro-
climate, air exchange rate, material emissions, artefact emissions,
infiltration). Thus, it is hard to assess the hazardous impact of VOCs
and emission levels detected within this study, as no alterations can
yet be traced back directly to the occurrence of VOCs [23]. Based on
the ALARA approach, the development of new concepts for exhi-
bition design, especially regarding ventilated showcases and the
integration of sorbent materials are necessitated as further steps.
Based on the work done by Grosjean and Parmar [46], future inves-
tigations have to focus on sorbent materials targeting on those
VOCs that are characteristic for museum showcases. Moreover,
a better knowledge both of interactions of pollutants with each
other and with artefact surfaces in complex scenarios like show-
cases are required in order to evaluate their potential hazardous
impact on movable cultural assets and in order to specify guideline
values.
Acknowledgements
The authors are grateful to all manufacturers for good coop-
eration. Financial support by the Stiftung Industrieforschung
Köln (project # S 727) is gratefully acknowledged. These
experimental series were also part of the Ph.D. thesis of A.
Schieweck [24]. Her special thanks go to the German National
Academic Foundation, Bonn, for a dissertation fellowship. The
authors thank also F. Fuhrmann, A. Schwarz, N. Siwinski and
D. Markewitz for their laboratory work and technical sup-
port.
References
[1] D. Camuffo, G. Sturaro, A. Valentino, Showcases: a really effective mean for
protecting artworks? Thermochimica Acta 365 (2000) 65–77.
[2] C.J. Weschler, H.C. Shields, Potential reactions among indoor pollutants, Atmo-
spheric Environment 31 (1997) 3487–3495.
[3] L.Sgt. Byne, The corrosion of shells in cabinets, Journal of Conchology 9 (1899),
pp. 172-178; 253-254.
[4] C.E. Miles, Wood coatings for display and storage cases, Studies in Conservation
31 (1986) 114–124.
[5] J. Tétreault, Display materials: the good, the bad, and the ugly, in: J.
Sage (Ed.), Preprint of the Conference of the Scottish Society for conserva-
tion and restoration (SSCR): exhibitions and conservation. Edinburgh, 1994,
pp. 79–87.
[6] A. Brokerhof, M. van Bommel, Deterioration of calcareous materials by acetic
acid vapour: a model study, in: J. Bridgeland (Ed.), Proceedings of ICOM, 11th
Triennial Meeting. Edinburgh, 1996, pp. 769–775.
[7] N.A. Katsanos, F. De Santis, A. Cordoba, F. Roubani-Kalantozopoulou, D. Pasella,
Corrosive effects from the deposition of gaseous pollutants on surfaces of cul-
tural and artistic value inside museums, Journal of Hazardous Materials 64
(1999) 21–36.
[8] A.L. Dupont, J. Tétreault, Cellulose degradation in an acetic acid environment,
Studies in Conservation 45 (2000) 210–1210.
[9] A. Niklasson, L.G. Johannson, J.E. Svensson, Influence of acetic acid vapor on
the atmospheric corrosion of lead, Journal of The Electrochemical Society 152
(2005) B519–B525.
[10] W.A. Oddy, An unsuspected danger in display, Museums Journal 73 (1973)
27–28.
[11] S.M. Blackshaw, V.D. Daniels, The testing of materials for use in storage and
display in museums, The Conservator 3 (1979) l6–l9.
[12] L.R. Green, D. Thickett, A new methodology for accelerated corrosion testing,
Studies in Conservation 48 (2003) 263–268.
 A. Schieweck, T. Salthammer / Journal of Cultural Heritage 12 (2011) 205–213
[13] L. Robinet, D. Thickett, Testing materials for use in the storage and display
of antiquities – a revised methodology, Studies in Conservation 40 (1995)
145–152.
[14] S. Hackney, The distribution of gaseous air pollution within museums, Studies
in Conservation 29 (1984) 105–116.
[15] C.M. Grzywacs, N.H. Tennent, Pollution monitoring in storage and display cabi-
nets: carbonyl pollutant levels in relation to artifact deterioration, Preprints
of the IIC Ottawa Congress, Preventive Conservation – Practice, Theory and
Research. Ottawa (1994) 164–170.
[16] O. Jann, O. Wilke, D. Brödner, U. Schneider, S. Marten, Die Umgebungsluft von
Exponaten, Restauro 106 (2000) 428–432.
[17] O. Hahn, O. Wilke, O. Jann, Indoor air quality in show cases – an attempt to stan-
dardise emission measurements, ZKK – Zeitschrift für Kunsttechnologie und
Konservierung 21 (2007) 275–279.
[18] P.B. Hatchfield, Pollutants in the museum environment, Archetype Publications
Ltd, London, 2002.
[19] A. Schieweck, B. Lohrengel, N. Siwinski, C. Genning, T. Salthammer, Organic
and inorganic pollutants in storage rooms of the Lower Saxony State Museum
Hanover Germany, Atmospheric Environment 39 (2005) 6098–6108.
[20] A. Schieweck, W. Delius, N. Siwinski, W. Vogtenrath, C. Genning, T. Salthammer,
Occurrence of organic and inorganic biocides in the museum environment,
Atmospheric Environment 41 (2007) 3266–3275.
[21] T. Salthammer, Environmental test chambers and cells, in: T. Salthammer, E.
Uhde (Eds.), Organic indoor air pollutants. Occurrence, measurement, evalua-
tion, 2nd ed., WILEY-VCH, Weinheim, 2009, pp. 101–115.
[22] A. Schieweck, D. Markewitz, T. Salthammer, Chemical substances in newly con-
structed showcases, ZKK – Zeitschrift für Kunsttechnologie und Konservierung
21 (2007) 280–286.
[23] A. Schieweck, T. Salthammer, Emissions from construction and decoration
materials for museum showcases, Studies in Conservation 54 (2009) 218–235.
[24] A. Schieweck, Airborne pollutants in museum showcases – material emissions,
influences, impact on artworks, in: Ph. D. thesis, Dresden Academy of Fine Arts,
Germany, 2009.
[25] E. Uhde, T. Salthammer, Impact of reaction products from building materials
and furnishings on indoor air quality – a review of recent advances in indoor
chemistry, Atmospheric Environment 41 (2007) 3111–3128.
[26] E. Uhde, Application of solid sorbents for the sampling of volatile organic com-
pounds in indoor air, in: T. Salthammer, E. Uhde (Eds.), Organic indoor air
pollutants. Occurrence, measurement, evaluation, 2nd ed., WILEY-VCH, Wein-
heim, 2009, pp. 3–18.
[27] F.W. McLafferty, F. Turecek, Interpretation of mass spectra, University Science
Books, Mill Valley, CA, 1993.
[28] E. Massold, C. Bähr, T. Salthammer, S.K. Brown, Determination of VOC and
TVOC using thermal desorption GC-MS – practical implications for test cham-
ber experiments, Chromatographia 62 (2005) 75–85.
213
[29] Anonymous, Diffusive uptake rates on PerkinElmer sorbent tubes, in: Health
and Safety Executive CAR Committee (Committee on Analytical Require-
ments), Working Group 5. The Diffusive Monitor 12, 2001, Available online
at http://www.hsl.gov.uk/publications/diffusive-monitor.html.
[30] S. Belman, The fluorimetric determination of formaldehyde, Anal. Chim. Acta
29 (1963) 120–126.
[31] R. Kellner, J.M. Mermet, M. Otto, M. Valcárcel, H.M. Widmer, Analytical Chem-
istry, WILEY-VCH, Weinheim, 2004.
[32] J.W. Einax, H.W. Zwanziger, S. Geiß, Chemometrics in environmental analysis,
WILEY-VCH, Weinheim, 1997.
[33] VDI 4300-7, Indoor-air pollution measurement – measurement of indoor air
change rate, Beuth Verlag, Berlin, 2001.
[34] G. Habenicht, Kleben – Grundlagen, Technologie, Anwendungen, Springer-
Verlag, Berlin Heidelberg, 1997.
[35] S. Bradley, D. Thickett, The pollution problem in perspective, in: J. Bridgland
(Ed.), Proceedings of ICOM, 12th Triennial Meeting. Lyon, 1999, pp. 8–14.
[36] P.D. Donovan, T.M. Moynehan, The corrosion of metals by vapours from air-
drying paints, Corrosion Science 5 (1965) 803–814.
[37] D. Fengel, G. Wegener, Wood, Walter De Gruyter, Berlin, 1989.
[38] M.R. Raychaudhuri, P. Brimblecombe, Formaldehyde oxidation and lead corro-
sion, Studies in Conservation 45 (2000) 226–232.
[39] P. Hatchfield, J. Carpenter, Formaldehyde: how great is the danger to
museum collections? Harvard University Art Museum, Cambridge, MA,
1987.
[40] D. Crump, Application of diffusive samplers, in: T. Salthammer, E. Uhde (Eds.),
Organic indoor air pollutants. Occurrence, measurement, evaluation, 2nd ed.,
WILEY-VCH, Weinheim, 2009, pp. 47–63.
[41] P. Wolkoff, How to measure and evaluate volatile organic compound emissions
from building products. A perspective, The Science of the Total Environment
227 (1999) 197–213.
[42] T. Salthammer, Emissions of volatile organic compounds from products and
materials in indoor environments, in: P. Pluschke (Ed.), Indoor Air Pollution.
The Handbook of Environmental Chemistry, 4F, Springer-Verlag, Berlin, 2004,
pp. 37–71.
[43] O. Wilke, O. Jann, D. Brödner, VOC- and SVOC-emissions from adhesives,
floor coverings and complete floor structures, Indoor Air 14 (Suppl. 8) (2004)
98–107.
[44] J. Tétreault, Coatings for display and storage in museums, in: CCI Technical
Bulletin 21, Canadian Conservation Institute, Ottawa, 1999.
[45] J. Tétreault, Airborne pollutants in museums, galleries, and archives: risk
assessment, control strategies, and preservation management, Canadian Con-
servation Institute, Ottawa, 2003.
[46] D. Grosjean, S.S. Parmar, Removal of air pollutant mixtures from museum dis-
play cases, Studies in Conservation 36 (1991) 129–141.