Article

pubs.acs.org/ac

Detection of Metabolites of Trapped Humans Using Ion Mobility

Spectrometry Coupled with Gas Chromatography
Wolfgang Vautz,*, Rafael Slodzynski, Chandrasekhara Hariharan, Luzia Seifert, Jurgen Nolte,
Rita Fobbe, Stefanie Sielemann, Bolan C. Lao, Ran Huo, C. L. Paul Thomas, and Lars Hildebrand

Leibniz-Institut fur Analytische WissenschaftenISASe.V., Bunsen-Kirchho-Strae 11, 44139 Dortmund, Germany

Gesellschaft fur analytische Sensorsysteme mbH (G.A.S.), Otto-Hahn-Strae 15, 44227 Dortmund, Germany

Department of Chemistry, Centre for Analytical Science, Loughborough University, LE11 3TU, United Kingdom

Department of Computer Science, University of Dortmund, Otto-Hahn Street 16, 44227 Dortmund, Germany

S Supporting Information
*

ABSTRACT: For the rst time, ion mobility spectrometry

coupled with rapid gas chromatography, using multicapillary
columns, was applied for the development of a pattern of signs of
life for the localization of entrapped victims after disaster events
(e.g., earthquake, terroristic attack). During a simulation
experiment with entrapped volunteers, 12 human metabolites
could be detected in the air of the void with sucient sensitivity
to enable a valid decision on the presence of a living person.
Using a basic normalized summation of the measured
concentrations, all volunteers involved in the particular experiments could be recognized only few minutes after they entered
the simulation void and after less than 3 min of analysis time. An
additional independent validation experiment enabled the
recognition of a person in a room of 25 m3 after 30 min with suciently high sensitivity to detect even a person briey
leaving the room. Undoubtedly, additional work must be done on analysis time and weight of the equipment, as well as on
validation during real disaster events. However, the enormous potential of the method as a signicantly helpful tool for searchand-rescue operations, in addition to trained canines, could be demonstrated.

region, professional urban search and rescue (USaR) teams are

mobilized at the national and eventually international level. It is
of essential importance to localize trapped victims as early as
possible, to avoid any decline in their vital status, even if they
are not directly injured. Furthermore, immediate and reliable
information on their health status would be of signicant
relevance to enable prompt inception of the particular
operations and to initiate focused medical support. Therefore,
USaR may be divided in four subsequent steps, and during all
of these steps, the safety of the rescuers must be guaranteed
continuously:6
(1) Localization of trapped bodies
(2) Assessment to determine if the trapped victim is still alive
(3) Monitoring of their vital statistics.
(4) Rescue and rst aid
For the rst step, the localization of trapped victims after a
disaster event, dogs still are the method of choice, because of
the extreme mobility and sensitivity of trained canines.
However, dogs need a break quite frequently and they have

earch and rescue of trapped humans is a permanent

challenge for teams specialized in this eld. Geological
events such as earthquakes, volcanic eruptions, or landslides
happen everyday.1 Most of these events are not perceived, since
their impact is too small. But the situation changes dramatically
if such phenomena strike urban areas.2 Every year, signicant
disasters occur, such as the recent earthquakes in Haiti3 and
Japan in 2011, sometimes followed by a severe tsunami. As a
consequence, buildings are destroyed and many people are
trapped in the ruins.4 Similar scenarios may happen after
tropical storms as well as events induced by terroristic attacks.4
In all cases, it is of essential importance to localize and rescue
the trapped victims as soon as possible to save their lives. Many
of them are severely injured and urgently need medical rst aid.
Although the equipment available for the search and rescue
teams is developing continuously, there is always a need for
further improvement.5
Time is the critical parameter during search-and-rescue
operations. In most instances, initial search-and-rescue
procedures are carried out by survivors.5 Then, re and police
departments and other local authorities will converge on the
aected area and assume control and coordination. In a largescale disaster that overwhelms the resilience of the aected
2012 American Chemical Society

Received: September 23, 2012

Accepted: December 18, 2012
Published: December 18, 2012
2135

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

TSG 4161). The CO2 concentration prole is used to visualize

the development of the particular experiments. It is the ideal
parameter for this purpose: because of the controlled
conditions, the only source of CO2 is the particular volunteer
in the void.
Ion Mobility Spectrometry Coupled with Gas Chromatography. Ion mobility spectrometry is a sensitive and
rapid analytical method for the detection of trace substances in
the gas phase.11 In the present study, analyte molecules are
ionized by proton transfer from reactant ions that are produced
by a -radiation source. In general, protonated monomer ions
are formed. However, when the concentration increases, dimers
or even higher polymer ions also may be formed.
The ions are accelerated by a weak electric eld toward the
detector, which is a Faraday plate. An ion gate is opened and an
ion cloud is allowed to enter the drift region, thus starting to
travel toward the detector. A drift gas ow in the opposite
direction (nitrogen or clean and dry air) causes collisions of the
ions with the present gas molecules. Hence, the ions reach a
constant resulting drift velocity, depending on their charge,
mass, and shape. The drift velocity is characteristic for every
analyte molecule and can be calculated from the measured drift
time at a known drift length. Normalizing the drift velocity to
the electric eld provides the ion mobility (K). A further
normalization to pressure and temperature leads to the socalled reduced ion mobility (K0), which is a unique
characteristic of the analyte and independent of the
experimental conditions.
Method development rst started in the 1960s with initial
military application for the detection of chemical warfare agents
and, later, for security purposes (e.g., at airports, for the
detection of explosives and drugs of abuse).11 During the past
decade, the method was adopted to various additional elds
(e.g., for air quality monitoring, process control, food quality
and safety, and for biological and medical purposes). In those
cases, samples are getting more and more complex and, in
particular, during the analysis of human breath, very humid. As
a consequence, the various analyte ions together with the water
molecules present at the same time in the ionization region
tend to form clusters, hence making their identication dicult
or even impossible. Therefore, ion mobility spectrometry
coupled with gas-chromatographic preseparation (GC/IMS)
has become more and more important.10,11
The instruments applied during the experiments described
above were both of that type: a custom-made research
instrument8 (ISAS, used for GC/IMS) and a commercial
instrument9 (BreathSpec, made by Gesellschaft fur analytische
Sensorsysteme mbH (G.A.S.), Dortmund, Germany). Both
instruments were equipped with a multicapillary column for
rapid gas-chromatographic preseparation (the ISAS system has
minimal polar capabilities, whereas G.A.S. does have polar
capabilities). They have already been applied successfully for
various applications (e.g., for the analysis of human breath,1214
as well as that of animal breath,15,16 and for the detection of the
metabolites of micro-organisms17,18 but also for food quality
and safety control1921 and for process control22,23).
For sampling, the room airparticularly, the air from the
void to be investigatedwas drawn for 20 s through the sample
loop to avoid memory eects. The volume of the sample loop
then was introduced into the preseparation column for analysis
using a six-way-valve. The instruments were operated with a
slightly dierent preseparation to enhance the information
obtained from the experiments. The full experimental setup,

problems in extremely dicult situations (e.g., with many dead

victims in the surroundings). Therefore, within the framework
of a joint research project funded by the European Union, we
intend to develop a Second Generation Locator for Urban
Search and Rescue, to improve the technical equipment for
search-and-rescue operations.
In particular, all available sensors, such as audio and video
(thermal, ultraviolet (UV), and visual cameras), should be
combined with innovative instruments such as ion mobility
spectrometers (IMS) or chemical sensor arrays. Furthermore,
all data obtained should be evaluated in a comprehensive way,
thus providing data of higher signicance related to the
detection of signs of life and even regarding the health status
of a trapped person. The innovative sensors include portable
ion mobility spectrometers for the detection of relevant volatile
organic compounds (VOCs) in the eld as available in a
commercial design7 but also laboratory instruments previously
used for the analysis of medical and biological applications,8 as
well as for food characterization.9 Those instruments combine
high sensitivity with rapid results in the range of secondsor
minutes, if additional gas-chromatographic preseparation is
applied.10 The work presented here is focused on the detection
of VOCs, which could enable the localization of trapped living
victims using ion mobility spectrometry with rapid gaschromatographic preseparation (GC/IMS). After optimization
and calibration procedures, two GC/IMS systems were applied
during the Trapped Human Experiment (abbreviated hereafter as THE),7 which was designed to simulate the situation of
victims trapped under collapsed buildings. A pattern of relevant
detected analytes was developed and veried during an
independent validation experiment.

EXPERIMENTAL SECTION
The Trapped Human Experiment. The Trapped
Human Experiment (THE) has previously been described in
detail.7 A continuously replenished reservoir of fresh air with a
reserve of almost 40 min was fed to a volunteer inside the
simulator representing a void in a collapsed building. The
volatiles released by the volunteer accumulated in the void and
were subsequently passed through a model of the debris: a glass
column containing cassettes of typical building materials. Each
cassette consisted of a set of disks made from materials
commonly used to construct a single story of a glass-clad,
reinforced-concrete building.
Altogether, 10 volunteers entered the void simulator for 6 h
each.7 All of them gave informed consent. The experiments that
we monitored for the safety of the volunteers for critical gas
concentrations and the health status of the volunteers were
recorded using a vital-signs monitor. Additional information on
the body-mass-index (BMI), the diet, medication, recent
digestion and on personal hygiene was collected directly from
the volunteers prior to the particular experiments. However,
only 7 of the particular experiments (Nos. 410) have been
completely investigated by GC/IMS and additionally TD-GC/
MS, starting in the last hour of experiment 3. GC/IMS and TDGC/MS samples were drawn directly from the void simulator
using 1-m Teon tubes. Note that none of the volunteers
urinated into the void, but volunteer 9 temporarily left the void
for this purpose.
During the THE, the environment in the void was controlled
for the safety of the volunteers. One of the variables that were
monitored continuously was the carbon dioxide concentration,
which was measured with an electrochemical sensor (Figaro
2136

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

lm thickness; Wicom, Heppenheim, Germany) was used for

compound separation with helium as the carrier gas at a
constant ow rate of 1.0 mL/min. The electron ionization
mode was performed with 70 eV, and a mass range of m/z 33
450 was detected.
To validate those proposals, the proposed analyte was
introduced in a HovaCAL (IAS, Frankfurt, Germany)
calibration gas generator26 for approval of the ion mobility
and retention time and for providing calibration curves for the
quantication.
Ethics. All volunteers during the THE, as well as those
involved in the studies at ISAS and G.A.S. laboratories, gave
written informed consent. The data was recorded, stored, and
evaluated anonymously. During all experiments, the volunteers
were medically controlled.

including the additional CO2 measurements, is described in

Table 1.
Table 1. Experimental Setup of Both GC/IMS Systems: ISAS
and G.A.S.a
parameter
owMCC
lengthMCC
temperatureMCC
typeMCC
ion source
lengthdrift
owdrift
temperaturedrift
electric eld
volumeloop
temperatureloop

ISAS GC/IMS
Preseparation
150 mL/min
20 cm
40 C
OV-5, min polar
IMS
63
Ni, 550 MBq
12 cm
100 mL/min
ambient
320 V/cm
Sampling
8 mL
40 C

G.A.S. BreathSpec
100 mL/min
20 cm
40 C
OV-1701, polar
3

H, 100 MBq
5 cm
500 mL/min
40 C
400 V/cm

RESULTS AND DISCUSSION

In the GC/IMS spectra obtained during the experiment,
altogether, 46 signals were investigated, all of them following
the development of the experiments and the CO2 slope in
particular, as discussed in the following in detail.
Octanal, as a rst example, was detected during all
experiments but with a higher concentration during one
particular experiment (No. 6) compared to the others. Octanal
has already been found in samples of human breath,27 which
explains the elevated concentration during the particular
experiment (see Figure 2). On the other hand, it is also used
as a solvent, which could be the reason for the elevated
concentration in experiment 6, where the volunteer declared
that a specic perfume was recently used. Not all signals
appeared during all experiments. From the additional data
obtained from the volunteers, one could assume that those
signals are related to individual digestion, diet, or personal
hygiene. Those signals cannot be expected for any trapped
person, and, therefore, those peaks were not considered for
further evaluation.
The signal of 4-methyl-2-pentanone was used for validation
of the correlation of the GC/MS analysis of the samples to the
GC/IMS data. This analyte is supposed to be present in paint
and glue and might be related to the construction of the void.
Therefore, a signicant increase could be observed during the

5 mL
40 C

CO2 reference measurements were made using the following

equipment and conditions: Figaro TSG 4161 sensor, operating
range = 010.000 ppm.

Identication and Quantication. For the identication

of the signals in the GC/IMS, their ion mobility24 and retention
time were compared to the values in the ISAS analyte database.
If no match could be found, related TD-GC/MS analyses of
samples from the void (1 L drawn by a pump via a Teon tube)
on TENAX adsorption tubes were consulted and, by using
appropriate alignment procedures25 for the GC/MS and GC/
IMS retention times, proposals on the origin of unknown GC/
IMS signals could be given.
For GC/MS analysis, the adsorbed analytes were desorbed
thermally and the sample was injected splitless at 250 C into
an Agilent Technologies Model 6890N GC system connected
with an Agilent Technologies Model 5973 mass-selective
detector (MSD, Gerstel, Muhlheim, Germany). The initial
oven temperature of 35 C was maintained for 2 min and then
increased to 250 C at a rate of 7 C/min and nally held for
27 min. A HP-5MS capillary column (60 m, 0.25 mm, 0.25 m

Table 2. Reduced Ion Mobility and Retention Time of the Analytes Considered as Signs of Life (Some Exemplary References
Are Indicated)
Detection Limit (ppb)
compound

data source

2-ethyl-1-hexanol
2,2,4,6,6-pentamethylheptane
acetone
acetophenone
ammonia
benzaldehyde
cumol (benzene, 1-methylethyl)
decanal
hexanal (capronaldehyde)
limonene
octanal
pelargonaldehyde (nonanal)

ref 28
ref 30
refs 28, 30
ref 28
ref 30
ref 28
ref 31
ref 27
ref 27
ref 29
ref 27
ref 27

reduced ion mobility, K0 (cm V

1.441
1.511
2.020
1.724
2.195
1.783
1.664
1.295
1.565
1.684
1.408
1.350

s )

retention time, tR (s)

dry sample

humid samplea

32.5
27.4
2.4
39.3
4.0
18.5
14.6
130.0
7.6
27.4
25.0
55.1

0.05
18
2
0.10
b
0.02
4
0.10
0.30
0.50
0.10
0.30

0.05
10
30
0.02
b
0.02
350c
0.1
10.00
1
0.1
0.3

a
c

100% relative humidity (RH). bAccurate calibration was not possible in the present setup. However, the concentrations are in the lower ppbV range.
40% RH (for higher humidity, the LOD is too high to provide reliable concentrations with the available calibration gas generator).
2137

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

The ion mobility and retention time values given in Table 2

cover a relatively wide range and the position of the particular
peaks is isolated. Therefore, their accurate quantication is
possible, because they do not overlap. The isolated analyte
peaks are presented in Figure 1; some of them even formed
dimer ions at the particular concentration level. This was
validated not only by calibrating the particular analytes
separately but also by measuring them together in a reference
mixture. However, in a real case, overlapping of the relevant
signs of life with signals from other trace substances available in
the ambient air on-site must be expected and must be
considered when conclusions are drawn from a measurement
on the probability of the presence of a living trapped victim.
This must be investigated in the future by applying the
proposed method during real disaster events.
During the THE, not all 12 analytes could be evaluated
properly, due to weak performance of the instrument after
recent transportation and high humidity in the void. Therefore,
acetone was not evaluated at allthe signal appears in the
shoulder of the reactant ion peak, which was broadened during
the experiment. Quantication of the ammonia peak was also
dicult, because the instrument was contaminated, to a certain
degree, with humidity, which overlaps the ammonia signal.
Nevertheless, the results obtained during the experiments are
compelling, as presented in the following discussion. Figure 2
presents the slope of the normalized concentration of the
selected human metabolites during experiments 410.
At least seven of the selected signs of life detected with the
GC/IMS show a clear correlation with the progress of the
experiment (see Figure 2A). Increasing concentrations can be
observed during the particular experiments, while a rapid drop
of concentration can be observed when the volunteers left the
void at the end of the particular experiment (the breaks are
indicated by the gray bars). The high uctuations during
experiment 4the rst one that was investigated completely
may be explained by the quite poor performance of the IMS
device shortly after transportation. Overall, it can be observed
that the slope of the dierent analytes show dierent
concentration maxima for each experiment. This is due to the
individual metabolism of the particular volunteers, including
inuencing parameters, such as diet, digestion, or personal
hygiene.
For validation of the conclusions drawn from the detection of
particular analytes identied as signs of life, all data were
compared to the slope of the CO2 concentration, as presented
in Figure 2D. After a steep increase of 60 min after the start of
a particular experiment, the CO2 concentration reaches a
plateau of 4000 ppm, which rapidly decreases again after the
volunteers have left the void 6 h later. During experiment 8, the
gas sensor system including CO2 was disconnected for
changing the sampling points, thus causing a temporary
decrease of concentration while both GC/IMS were still
connected to the void. During experiment 9, the volunteer
temporarily left the void to urinate, which can also be detected
by a breakdown of concentration in the CO2 prole.
For the controlled experiments of the THE, the trapped
volunteers were the only source of CO2; therefore, the CO2
slope can be considered as the ultimate sign of life for the
simulation setup. In real disaster events, this is not necessarily
true, because CO2 could also be derived from combustion or
res. However, all seven analytes clearly follow the slope of
CO2 (see Figures 2A and 2D) and, hence, can be considered as
reliable signs of life.

experimentsmost probably due to accumulation in the closed

voidwith good agreement with the GC/MS analysis.
To obtain information on the concentration range of the
detected analytes, the GC/IMS was calibrated with reference
analytes using the HovaCAL calibration gas generator.26 In
general, all relevant analytes are detected in the lower ppbV
range, down to the pptV level, with varying eect of humidity.
However, accurate quantication of those analytes in a real case
may be dicult, since, in many cases, the GC/IMS response is
dependent on the humidity of the sample. Therefore, the limits
of detection (LODs) are given in Table 2 for dry and for humid
(100% relative humidity (RH)) samples, to demonstrate the
variance of the values. However, by optimizing the experimental
setup, the limits of detection may be improved signicantly for
a particular or distinct pattern of analytes.
Furthermore, in complex and humid samples, peaks may
overlap in retention time and, therefore, are competing for the
protons provided by the reactant ions, thus further impeding
quantication. Therefore, in the following, we do not display
the concentration but rather the concentration values
normalized to the maximum value during the experiments,
since the focus is on the comparison of the slope of those signs
of life. Moreover, during real disaster events, the background
concentration may vary signicantly. Under such conditions, it
is more important to detect concentration changes than the
accurate absolute value. In the following, we present the values
obtained from the ISAS GC/IMS only to avoid negative
inuence on the correlation to the experiments by the slightly
dierent performance of both ISAS and G.A.S. instruments.
However, both instruments obtained comparable results with
only minor deviations, most probably due to dierent
experimental setups.
Finally, 12 analytes that are already reported to be available
in human breath in the literature (see Table 2, some exemplary
references are indicated)independent of whether studies
compared cancer/noncancer or smoker/nonsmoker groups
were chosen to represent a human presence. Furthermore,
those analytes have already been detected in human breath
during many investigations of the authors group. All 12
substances have been observed during all experiments with a
concentration slope related to the experiments or to CO2. The
selected analytes (see Table 2) are giving the characteristic
pattern of signs of life, as presented in Figure 1.

Figure 1. Signs of life pattern (12 human metabolites) as detected

using ion mobility spectrometry coupled with gas chromatography
(GC/IMS) for the localization of trapped victims. Some of the
analytes even formed dimer ions at the particular concentration level.
2138

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

Figure 2. Slope of the human metabolites selected as signs of life, as detected during the Trapped Human Experiment (THE) with GC/IMS (A, B,
C), and the slope of CO2 concentration, together with the normalized summation of the signs of life (D). The particular experiments and the breaks
are indicated.

Figure 2B shows the slope of three additional analytes

initially considered as signs of life but with a less clear

correlation to CO2. This might be due to the performance of

the instrument as already mentioned previously for ammonia
2139

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

Figure 3. General slope of concentration for a low initial concentration combined with a decreasing (Case I) and an increasing emission rate (Case
II).

Figure 4. The increase of the summation parameter, interpreted as a sign of life during the validation experiment (bold black line), is in excellent
agreement with the presence of the volunteer (bold gray line), including two occasions, at 14:50 and 15:40, when the volunteer briey left the room.

and acetone. However, they are veried human metabolites

and, therefore, will be included in the pattern of signs of life in
the following.
The slope of hexanal, as presented in Figure 2C, shows a
completely dierent behavior than the other analytes
mentioned above. Instead of a steep increase as observed
previously, the slope starts with a very slight increase with time.
Under the controlled condition of the human experiment, a
modeling of the slopes can be carried out quite simply. The air
in the void was exchanged with a continuous ow of fresh air,
for the safety of the volunteers. As a consequence, the
development of the concentration in the void depends on the
temporal development of the analyte emission rate or, in our
case, the exhalation of the entrapped volunteers, respectively.
Two dierent cases presented in Figure 3 show the general
behavior of the concentration slope when starting with a low
value for a decreasing emission rate (Case I) and an increasing

emission rate (Case II). For example, for CO2, it can be

expected that the volunteer will relax after a while in the void
some of them even fell asleepthus reducing the turnover of
inhaled and exhaled air, followed by a decreasing emission rate.
This is obviously true for all of the selected metabolites, except
for hexanal. In this case, the emission rates evidently increased
during the particular experiments. For many years, hexanal has
been known as a metabolite of lipid peroxidase and is related
closely to oxidative stress.32,33 An intensication of this process
caused by the special situation of the volunteer could explain
the signicant concentration slope during all particular
experiments.
For a realistic application of the proposed pattern of signs of
life for the search for victims in real disaster events, an
evaluation of each particular analyte included in the pattern is
not suitable. Therefore, a bulk parameter must be used as
output of such measurements, giving the information to the
2140

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

USaR teams if there is a living victim in an investigated void or

at least to what probability this could be the case. In a rst and
simple approach, we used the mean value of the normalized
concentrations for this purpose. Figure 2D shows the slope of
this normalized summation parameter, together with the CO2
concentration. It is evident that the presence of each individual
volunteer in the void of the THE would have been recognized
at least after 30 min from the increase of this parameter. For
example, using a threshold value of 0.4, all volunteers would
have been identied in the void without false alarms. Hence, in
real cases, an increase in concentration, compared to the
background level, will be the measure for an alarm.
However, the background concentration levels will undergo
signicant changes, especially when switching from a controlled
laboratory entrapment simulation to real disaster events.
Therefore, we carried out rst validation experiments at ISAS,
which is still not realistic but independent from the THE, with
respect to the void, the volunteers, and the equipment. The
room air was monitored during the day and the pattern of signs
of life was supposed to indicate when somebody was in the
room with a volume of 25 m3 for a while. Again, the room air
was drawn through the sample loop of the IMS (8 mL) to avoid
contamination and then was introduced into the multicapillary
column for preseparation. Indeed, after closing the door, a
signicant increase of the particular analytes included in the
signs of life pattern could be observed (see Figure 4); some of
them are indicated exemplarily as ne lines. The summation
parameter, which is calculated as the mean value of the
normalized concentration of all selected analytes, perfectly
describes the presence of the volunteer. Even two periods,
when the person left the room for a few minutes, are mirrored
by the slope of the summation parameter at 14:50 and 15:40.

facilitate the application in a pathless area. In parallel, further

validation experiments have to be carried out under realistic
conditions, e.g., in cooperation with the responsible search-andrescue organizations after a real disaster event. Only with data
obtained under such conditions can the optimal evaluation
algorithm be developed. This does not necessarily have to be
the presented normalized summation parameter: the dierent
analytes under consideration may have to be weighted.
Potentially, the result given from such an analysis must be
transferred to a probability of the presence of a living victim.
However, after these steps, the application of GC/IMS will
establish a signicantly helpful tool for search-and-rescue
operations, in addition to trained canines. Furthermore, since
the potential of IMS for medical diagnosis was recently
demonstrated in the literature, the instrument used for
localization of trapped victims might be used afterward for an
instant overview of the health status of the victim by breath
analysis.

CONCLUSIONS
From the simulations of the Trapped Human Experiment
(THE) and an additional independent validation experiment, it
could be demonstrated that, when using ion mobility
spectrometry coupled with gas chromatography (GC/IMS),
relevant human metabolites could be detected with sucient
sensitivity and selectivity to indicate the presence of living
trapped persons for the rst time. Altogether, 12 analytes,
which have already been veried as human metabolites in the
literature, could be used for the identication of trapped
humans after pattern recognition in the GC/IMS dataset onsite and immediately after the analysis of a sample drawn from a
void. A short-term increase in the concentration of a
normalized summation parameterin a real case, this is
determined by comparison of background concentrations with
those measured in a voidenables the identication of living
trapped humans. Because of the rapid preseparation when using
multicapillary columns, the analysis time with the present
experimental setup is <3 min.
However, the next step has to be further optimization of the
experimental parameters, with regard to sensitivity and
selectivity of the detected data and to the time required for
the analysis. In particular, the interference of the signals related
to the signs of life and others, depending on the environment,
the particular conditions during a disaster event, probably
accompanied by res and emissions from destroyed industrial
facilities or storage complexes, has to be considered and may
require further optimization.
Furthermore, the weight (presently, 25 kg, including gas
supply and batteries for 3 h of operation) must be reduced to

Notes

ASSOCIATED CONTENT

S Supporting Information
*

This material is available free of charge via the Internet at

http://pubs.acs.org.

AUTHOR INFORMATION

Corresponding Author

*Tel.: ++49-231-1392169. Fax: ++49-231-1392120. E-mail:

wolfgang.vautz@isas.de.
Author Contributions

The manuscript was written through contributions of all

authors. All authors have given approval to the nal version of
the manuscript.

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We want to acknowledge the excellent preparation and
performance of the Trapped Human Experiment by the
Centre for Analytical Science, Department of Chemistry at
Loughborough University, U.K. Last but not least, we are
grateful for the invaluable linguistic support by Jana Vautz. This
research was funded by the European Union as part of the
project Second Generator Locator for Urban Search and
Rescue (SGL for USaR). SGL for USaR was a collaborative
project (No. 217967) funded under call identier FP7-SEC2007-1, which is part of the Seventh Framework Program.
Furthermore, nancial support of the Bundesministerium f ur
Bildung and Forschung and the Ministerium fur Innovation,
Wissenschaf t and Forschung des Landes Nordrhein-Westfalen is
gratefully acknowledged.

NOMENCLATURE

Abbreviations

IMS
MS
GC
MCC
TD
VOC
THE
USaR
2141

ion mobility spectrometer

mass spectrometry
gas chromatography
multicapillary column
thermal desorption
volatile organic compound
trapped human experiment
urban search and rescue
dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142

Analytical Chemistry

Article

Parameters

(29) Cai, X.-J.; Block, J. E.; Uden, P. C.; Quimby, B. D.; Sullivan, J. J.
J. Agric. Food Chem. 1995, 43 (7), 17511753.
(30) Wang, C.; Sahay, P. Sensors 2009, 9, 82308262.
(31) Kushch, I.; Schwarz, K.; Schwentner, L.; Baumann, B.; Dzien,
A.; Schmid, A.; Unterkofler, K.; Gastl, G.; Spanel, P.; Smith, D.;
Amann, A. J. Breath Res. 2008, 2, 126.
(32) Keller, J. N.; Pang, Z.; Geddes, J. W.; Begley, J. O.; Germeyer,
A.; Waeg, G.; Mattson, M. P. J. Neurochem. 1997, 69, 273284.
(33) Montgomery, J. A.; Jette, M.; Huot, S.; des Rosiers, C. Biochem.
J. 1993, 294, 727733.

K ion mobility
K0 reduced ion mobility

REFERENCES

(1) USGSList of all earthquakes of the past 7 days (http://

earthquake.usgs.gov/earthquakes/map/). Accessed December 3, 2012.
(2) Ramirez, M.; Peek-Asa, C. Epidemiol. Rev. 2005, 27 (1), 4755.
(3) WHO: Public health risk assessment and interventions.
Earthquake: Haiti, January 2010 (http://site.ebrary.com/lib/disaster/
docDetail.action?docID=10370951&p00=
earthquake%20earthquakes). Accessed December 3, 2012.
(4) Kean, T. H., Ed. The 9/11 Commission Report; W. W. Norton &
Co., Ltd.: New York, 2004.
(5) Wong; J., Robinson, C. Urban Search and Rescue Technology Needs
Identication of Needs; U.S. Department of Homeland Security/FEMA:
Washington, DC, 2004.
(6) Statheropoulos, M.; Sianos, E.; Agapiou, A.; Georgiadou, A.;
Pappa, A.; Tzamtzis, N.; Giotaki, H.; Papageorgiou, C.; Kolostoumbis,
D. J. Chromatogr., B 2005, B822, 112117.
(7) R. Huo, R.; Agapiou, A.; Bocos-Bintintan, V.; Brown, L.; Burns,
C.; Creaser, C. S.; Davenport, N.; Guallar-Hoyas, C.; Hildebrand, L.;
Malkar, A.; Martin, H.; Moll, V. H.; Patel, P.; Ratiu, A.; Reynolds, J. C.;
Sielmann, S.; Slodzynski, R.; Statheropoulos, M.; Turner, M.; Vautz,
W.; Wright, V.; Thomas, C. L. P. J. Breath Res. 2011, 5, 112.
(8) Vautz, W.; Baumbach, J. I. Int. J. Ion Mobility Spectrom. 2008, 11
(14), 3541.
(9) Garrido-Delgado, R.; Mercader-Trejo, F.; Sielemann, S.; de
Bruyn, W.; Arce, L.; Valcarcel, M. Anal. Chim. Acta 2011, 696, 108
115.
(10) Borsdorf, H.; Mayer, T.; Zarejousheghani, M.; Eiceman, G. A.
Appl. Spectrosc. Rev. 2011, 46, 472521.
(11) Eiceman, G. A.; Karpas, Z. Ion Mobility Spectrometry; Taylor and
Francis/CRC Press: Boca Raton, FL, 2005.
(12) Westhoff, M.; Litterst, P.; Freitag, L.; Urfer, W.; Bader, S.;
Baumbach, J. I. Thorax 2009, 64 (9), 744748.
(13) Vautz, W.; Nolte, J.; Fobbe, R.; Baumbach, J. I. J. Breath Res.
2009, 3 (3), 036004-1036004-8.
(14) Perl, T.; Carstens, E. T. H.; Hirn, A.; Quintel, M.; Vautz, W.;
Nolte, J.; Junger, M. Br. J. Anaesth. 2009, 103 (6), 822827.
(15) Vautz, W.; Nolte, J.; Bufe, A.; Baumbach, J. I.; Peters, M. J. Appl.
Physiol. 2010, 108 (3), 697704.
(16) Neuhaus, S.; Seifert, L.; Vautz, W.; Nolte, J.; Bufe, A.; Peters, M.
J. Appl. Physiol. 2011, 111 (4), 10881095.
(17) Junger, M.; Vautz, W.; Kuhns, M.; Hofmann, L.; Ulbricht, S.;
Baumbach, J. I.; Quintel, M.; Perl, T. Appl. Microbiol. Biotechnol. 2012,
93 (6), 26032614.
(18) Perl, T.; Junger, M.; Vautz, W.; Nolte, J.; Kuhns, M.; Borg-von
Zepelin, M.; Quintel, M. Mycoses 2011, 54 (6), e828e837.
(19) Vautz, W.; Baumbach, J. I.; Jung, J. J. Inst. Brew. 2006, 112 (2),
157164.
(20) Vautz, W.; Zimmermann, D.; Hartmann, M.; Baumbach, J. I.;
Nolte, J.; Jung, J. Food Addit. Contam. 2006, 23 (11), 10641073.
(21) Garrido-Delgado, R.; Arce, L.; Guaman, A. V.; Pardo, A.; Marco,
S.; Valcarcel, M. Talanta 2011, 84 (2), 471479.
(22) Vautz, W.; Mauntz, W.; Engell, S.; Baumbach, J. I. Macromol.
Reaction Eng. 2009, 3 (23), 8590.
(23) Vautz, W.; Baumbach, J. I. Eng. Life Sci. 2008, 8 (1), 1925.
(24) Vautz, W.; Bodecker, B.; Baumbach, J. I.; Bader, S.; Westhoff,
M.; Perl, T. Int. J. Ion Mobility Spectrom. 2009, 12 (2), 4757.
(25) Perl, T.; Bodeker, B.; Junger, M.; Nolte, J.; Vautz, W. Anal.
Bioanal. Chem. 2010, 397 (6), 23852394.
(26) Vautz, W.; Schmah, M. Int. J. Ion Mobility Spectrom. 2009, 12
(4), 139147.
(27) Fuchs, P.; Loeseken, C.; Schubert, J. K.; Wolfram Miekisch, W.
Int. J. Cancer 2010, 126, 26632670.
(28) Hanai, Y.; Shimono, K.; Oka, H.; Baba, Y.; Yamazaki, K.;
Beauchamp, G. K. Cancer Cell Int. 2012, 12 (7), 113.

NOTE ADDED AFTER ASAP PUBLICATION

This paper was published on the Web on January 8, 2013.
Additions were made to the author list as well as a revision to
the Acknowledgment, and the corrected version was reposted
on February 7, 2013.

2142

dx.doi.org/10.1021/ac302752f | Anal. Chem. 2013, 85, 21352142