LAUNDRY

CHAMILA J. DENAWAKA, IAN A. FOWLIS, KATHERINE STAPLETON, JOHN R. DEAN*

*Corresponding author
Northumbria University, Department of Applied Sciences, Newcastle upon Tyne NE1 8ST, United Kingdom

John R. Dean

Gas chromatography
and associated techniques
in the analysis of laundry malodour
KEYWORDS: malodour, laundry, gas chromatography, ion mobility spectrometry, mass spectrometry

Abstract This paper reviews the use of chromatography in the identification of malodour in laundry. Two
approaches are described: the first involves the use of the traditional approach of gas chromato-
graphy mass spectrometry while the second approach uses a new approach based on multi-capillary column gas chromatography
ion mobility spectrometry (MCC-GC-IMS). Examples of GC-MS data representative of the volatile compounds associated with the
inside of a washing machine are shown. MCC-GC-IMS has the advantages of extreme sensitivity for volatile compounds as well as the
ability to detect nitrogen and sulphur containing molecules. Finally, selected examples of the application of chromatography for the
analysis of malodour are presented.

INTRODUCTION that it is a high resolution technique, that is that will separate

The science of laundry is complex and at Northumbria
University we have been applying new technologies to
attempt to understand the extent of the generation of
malodour during human activity and also to follow the removal
of the associated compounds in washing processes. This also
necessitated a study of the generation of malodours in washing
machines which are also a by-product of human activity. Our
sense of smell is generally well developed although there is a
tendency for it to degenerate in later life. It is fortunate that this
is the case since the range of smells which we encounter not
only may give us pleasure but in addition sometimes provide
warnings of possible dangers or unpleasant environments. So
what are smells and odours?
Although single organic compounds frequently have
characteristic odours by which we are often able to identify
them, the aromas and odours associated with plants, animals
and everyday life generally are not single compounds but are
a mix of different sizes of molecules and of different classes
of organic compounds with varying compositions. One thing
that they all have in common is the fact that the compounds
involved are all present in the vapour phase at ambient
temperatures and pressures. After all if they were not volatile
we would not smell them. A perfume, either natural or synthetic,
may be made up of several hundred individual compounds.
Malodours generally comprise fewer compounds.
In analytical chemistry we can usually work on the basis that
if we can smell something then we can analyse it using gas
chromatography. Gas chromatography also has the advantage
mixtures of compounds into their individual components, the
resulting separation being presented as a chromatogram. Gas
chromatography alone will not, however, identify the individual
compounds separated in the analysis but requires a specific
detection system at the exit of the gas chromatographic
column, for example, mass spectrometry.
GENERATION OF MALODOURS
Malodour is defined as an olfactory stimulant which when
detected is considered to be offensive to the individual. Common
malodours are often attributed to poor personal hygiene
including halitosis (1) and sweat (2) as well as damp clothing
after laundry (3, 4). It is well known that bacteria emit a wide
range of volatile organic compounds (VOCs). Therefore, it is not
unreasonable to postulate that bacteria that have colonised
washing machines could contribute to any malodour associated
with both the machine itself and clothing washed in it (3).
The generation of malodour on the various parts of the body
for example foot, underarm, hair or mouth are mainly due to
microbial transformation of odourless substances into malodour
volatile compounds. In addition to microbial activities, a number
of factors such as gender, genetic, environmental factors,
diseases, human activities, habits, diet, aging groups and ethic
group also influence body odour (2, 5). During wearing, fabrics
can be contaminated by sebaceous lipids, sweat, and dead
skin cells. These substrates provide the nourishment and facilitate
micro-organism survival on laundries (6, 7).

14 H&PC Today - Household and Personal Care Today, Vol. 9 nr. 4 July/August 2014
Numerous factors have been identified for the formation of is observed that while many components are identified (in this
malodour in laundries such as humidity, drying time, chemical case by a peak number) their identification (by GC-MS) and
oxidation and metabolism of micro-organisms as well as human odour (by GC-OD) is often inconclusive and non-correlated.
odour. Limited studies have been carried out to investigate the For example, the identification of a compound via the GC-MS
bacterial colonisation (biofilms) in washing machines (8, 9). In database does not necessarily correlate with the known odour
household washing machines, microbial survival followed by of that compound (as determined by the human nose, using
biofilm formation can occur due to soiled garments and poor GC-OD). Bacteriological assessment of samples taken from the
water treatments. A number of microbe species have been areas of interest in the washing machine was carried in order to
isolated and identified from the biofilm within washing machines assess whether there was a correlation between malodour and
(3, 8, 9). Among the different parts of a washing machine, hot bacterial contamination (9).
spots (i.e. product drawer, sump and rubber seal) of biofilm
formation are identified (9). Moreover it has been shown (9)
that a possible link exists between contamination of fabrics
in washing machines and the bacteria identified in washing
machine seals. This study identified potential VOC markers for
both high levels of bacteria and malodour in washing machines
as dimethyl disulphide and dimethyl trisulphide.

GAS CHROMATOGRAPHY MASS SPECTROMETRY

Apart from olfactory assessment of odours all other methods

have been chromatography based. Capillary column gas
chromatography with mass spectrometry detection (GC-MS)
is widely used in chemical analysis having the advantage
of providing component separation on the high resolution
chromatographic column and identification based upon the
fragmentation pattern generated in the mass spectrometer for
each individual peak as they are eluted from the column.
Unfortunately, even with the high sensitivity of analytical
equipment the concentration of many of the components in
odour samples is too low to allow identification based upon the
simple injection of a vapour sample, thus pre-concentration
methods are often necessary prior to analysis:
Solid phase micro extraction (SPME) is one such technique
where a silicon fibre coated with an adsorbent is placed in to
the headspace of the odour. The VOCs are adsorbed building
up an enhanced concentration and the fibre then injected into
the heated injection port of the GC from which the components
are eluted into the chromatographic column for subsequent
analysis. This static headspace method can be automated.
Thermal desorption (TD) is an alternative approach that involves
passing a stream of gas through the tube containing the sample
and then into an external Tenax adsorption tube. This can be
a more exhaustive method with greater pre-concentration of
analytes being possible. The adsorption tube is subsequently
heated and desorbed onto the GC column, hence the term
thermal desorption.
A further useful option with these methods is the possibility of
splitting the column effluent into two; sending one part to the
detector and the other to an outlet tube where a trained
chemist can frequently identify compounds eluting from
the column by the smell (a technique called GC-Olfactory
Detection, GC-OD).
Example chromatograms resulting from dynamic headspace
sampling of the atmosphere in selected areas (i.e. product
drawer, sump, drum and rubber seal) of a domestic washing
machine, thought to give rise to malodour on washed fabrics,
concentrated using Tenax adsorption tubes and thermal
desorption analysis are shown in Figure 1. The complexity of
the interpretation of the chromatograms obtained is illustrated
in Table 1. Table 1 summarises the (potential) identification
Figure 1. GC-MS chromatograms from a washing machine:
of the 53 components shown in Figure 1 after simultaneous
(A) product drawer, (B) sump, (C) drum and (D) rubber seal.
analysis by GC-MS fitted with an olfactory detector (GC-OD). It

H&PC Today - Household and Personal Care Today, Vol. 9 nr. 4 July/August 2014 15
 Table 1. Gas
chromatography
– olfactory
detection / mass
spectrometry
analysis of the
atmosphere in
selected areas
of a washing
machine (A)
Product Drawer,
(B) Sump, (C)
Drum, and (D)
Rubber Seal.

Key to terms:
GC-OD = gas
chromatography
– olfactory
detection;
GC-MS = gas
chromatography
– mass
spectrometry;
RT = retention
time of volatile
organic
compound;
No. = number
of peak on
chromatogram
(Figure 1); * good
MS library match,
+ tentative
identification
via MS library;
I = olfactory
intensity of
identified peak
termed weak
(W), medium
(M) and strong
(S); ND = not
detectable
peak; unknown =
a peak is present
but not possible
to identify from
MS databases.

16 H&PC Today - Household and Personal Care Today, Vol. 9 nr. 4 July/August 2014
MULTI-CAPILLARY COLUMN GAS CHROMATOGRAPHY ION
MOBILITY SPECTROMETRY
In this section our experience with much more recent
technology, multi-capillary column gas chromatography
combined with ion mobility spectrometry detection, MCC-
GC-IMS, to the application of malodour analysis will be
considered. An IMS instrument is compact, ideal for use in
the field, relatively simple to operate, sensitive, generally not
requiring pre-concentration methods and produces results very
rapidly. IMS instruments are widely used by security operations in
addition to the military and can frequently be seen in television
documentaries based upon airport security and import controls.
In recent years IMS has been combined with, for example, gas
chromatography (GC) (10). Gas chromatography combined
with ion mobility spectrometry extends the usefulness of IMS by
providing the additional dimension of retention time separation
of the gas chromatograph with the drift time separation of
the spectrometer. Further, the IMS signal intensity, provides
quantitative data in addition to the qualitative information. Thus
there are two types of separation, the first is chromatographic
separation and the second drift separation (Figure 2).
conditions (see for example, Figure 3). Although there is no
fragmentation of ions in IMS, since it is a soft ionization technique,
there is normally more than one response to the presence of a
compound ion, these are referred to as monomers, dimers and
trimers. These dimers and trimers are not the same as the dimers
and trimers in the conventional chemical sense but indicate
more than one ion species to be present in a water cluster with
the whole still having a single charge. [Note: monomers, dimers
and trimers appear at the same retention time for a particular
compound and are useful for confirmation of identity.] Detection
limits for the technique are typically in the low ppb range for volatile
compounds MCC-GC-IMS has an added advantage in that it will
detect very small molecules containing nitrogen or sulphur which
are not normally detectable by other GC detection modes.

Figure 3. Two-dimensional maps of 8 VCs separated by MCC-IMS.

Figure 2. 2D (A) and 3D (B) data visualisation using static

headspace sampling MCC-GC-IMS: Example topographic
view for formation of monomer (M) and dimer (D) for
1-butanethiol (100 ng).
RIP = reactive ion peak [for further details on the
interpretation of MCC-GC-IMS chromatograms and the
theory behind the technique please see reference (10)]

Table 2. Summary of malodour studies

As a means of providing a rapid confirmation of identity of
compounds detected on the two dimensional plot normally
used, map type presentations based upon co-ordinates
for known compounds of interest, i.e., retention time and
drift time, have been established for each set of operating
Key to terms: HS = headspace; SPME = solid phase
microextraction; GC = gas chromatography; MS = mass
spectrometry; DHS = dynamic headspace; OD = olfactory
detection; SHS = static headspace sampling; MCC =
multicapillary; IMS = ion mobility spectrometry; TD = Thermal
desorption; AED = atomic emission detector.

18 H&PC Today - Household and Personal Care Today, Vol. 9 nr. 4 July/August 2014
SUMMARY
A range of gas chromatography techniques have been
used to investigate malodour associated with the laundry
process i.e. the washing machine itself and soil garments. As
has been considered above the interpretation of the data
obtained is often complex. A summary of the research that
has been undertaken in the area of malodour identification
using gas chromatography is shown in Table 2. While some
researchers have identified some specific compounds
linked to malodour e.g. dimethyl disulphide and dimethyl
trisulphide (9,11) and 4-methyl-3-hexenoic acid (4,14)
uncertainty is still evident.
REFERENCES AND NOTES
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“Comparison of the Volatile Organic Compounds Present
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3. Munk, S., Johansen, C., Stahnke, L. H., Adler-Nissen,
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