Analytica Chimica Acta 1154 (2021) 338227

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Analytica Chimica Acta

journal homepage: www.elsevier.com/locate/aca

Detection of illegal treatment of table tennis rackets using gas

chromatography coupled to ion mobility spectrometry e A feasibility
study
Carolin Drees a, Markus Knieb a, b, Annika Fechner a, Joachim Franzke a, Claudia Herweg c,
Wolfgang Vautz a, d, *
a
Leibniz-Institut für Analytische Wissenschaften e ISAS e e.V., Bunsen-Kirchhoff-Straße 11, 44139, Dortmund, Germany
b
Hochschule Hamm-Lippstadt, Marker Allee 76-78, 59063, Hamm, Germany
c €ln, Germany
International Table Tennis Federation, Kaesenstr. 17, 50677, Ko
d
ION-GAS GmbH, Konrad-Adenauer-Allee 11, 44263, Dortmund, Germany

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Ion mobility coupled to gas chroma-

tography (GC-IMS) enables booster
control in table tennis.
 Characteristic VOC patterns of table
tennis coverings and from boosters
can be differentiated.
 Quantitative and selective determi-
nation of relevant compounds by
calibration.
 Short analysis time (1e2 min) using
mobile GC-IMS allows booster
monitoring on-site.
 This analytical tool GC-IMS could
help keeping sports fair and
equitable.

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

Article history: In all professional sports, performance pressure is high at the top level. Therefore, rules are defined and
Received 14 October 2020 controlled to keep sports fair in accordance e.g. with the Agenda 21 of the International Olympic
Received in revised form Committee. However, it’s about money and honour and as a consequence it is obvious that the athletes
14 January 2021
will go to the limits at all levels or even beyond. This is not only true for performance-enhancing sub-
Accepted 17 January 2021
Available online 21 January 2021
stances to improve the physical capacity but e when sports equipment is involved e also for their
optimisation. Thus, rules and related controls are necessary with regard to fairness between competitors
but also with regard to their health when chemicals are involved. In table tennis, such chemicals (so-
Keywords:
Ion mobility spectrometry
called boosters) are used occasionally e but against the rules e to improve the performance of the
Gas chromatography rackets. In the present study, several boosters were analysed as well as numerous common racket
Table tennis racket coverings using ion mobility spectrometry coupled to gas-chromatographic pre-separation. After opti-
Booster misation of sampling with regard to improving reproducibility, characteristic patterns of volatiles for
Softening agents booster compounds and for racket coverings with different characteristics were developed successfully.
Method development In particular, signals related to particular softening agents could be identified and detected even in the

* Corresponding author. Leibniz-Institut für Analytische Wissenschaften e ISAS e

e.V., Bunsen-Kirchhoff-Straße 11, 44139, Dortmund, Germany.
E-mail addresses: [email protected] (C. Drees), [email protected] (M. Knieb),
[email protected] (A. Fechner), [email protected] (J. Franzke),
[email protected] (C. Herweg), [email protected] (W. Vautz).

https://doi.org/10.1016/j.aca.2021.338227
0003-2670/© 2021 Elsevier B.V. All rights reserved.
C. Drees, M. Knieb, A. Fechner et al. Analytica Chimica Acta 1154 (2021) 338227

untreated coverings. The patterns of volatiles were found to be characteristic for the particular boosters
investigated as well as for the particular coverings. Furthermore, those patterns enable a differentiation
between booster and covering or e in other words e between rule-consistent racket coverings and rule
violation by after treatment of the rubber with a booster. After adaptation of the entire procedure to
realistic competition situations, the method could be used for proving an infringement against the
prohibition of applying such compounds.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction applications where VOC patterns are relevant, such as medical

diagnosis and therapy control [6,7], forensics [8], microbial appli-
Any game is characterised by rules set on how the players have cations [9,10] or process and quality control [11,12]. Furthermore,
to behave and by what is allowed or what is prohibited under GC-IMS has already been used for detecting illegal additives in
penalty. This is the declared goal of all specific organisations as for liquids as shown by Budzynska et al. for e-liquids used in electronic
example documented by the Agenda 21 of the International cigarettes [13].
Olympic Committee (see www.olympic.org). In any organised The objective of the present study was to find characteristic
sports and especially at the professional level, performance pres- patterns of VOCs from the racket surface and different patterns
sure is very high e due to the allocation of sponsoring and prize from the compounds in the boosters, thus enabling a rapid on-site
money in the top level. Therefore, a strong temptation to go to the control for irregular racket covering treatment, for e.g. immediately
limits of the rules is obvious and occasional attempts to even break after a particular table tennis match.
the rules is consequential. Doping is the most prominent example, It is obvious, that the background pattern of VOCs detected from
where athletes use prohibited compounds to improve their phys- the racket surface depends on the composition of the elastomer
ical performance [1]. Nevertheless, not only physical doping takes additives and intentionally introduced substances during produc-
place, but, if personal sport equipment is involved in the game, tion. However, on one hand we could not obtain any information
there is also a danger of prohibited treatment or irregular charac- about this composition and furthermore, the goal of this feasibility
teristics of those tools. For example, in ski jumping, there are exact study was to detect compounds characteristic for the boosters used.
specifications for skiing suits or in Formula 1 for all performance Certainly, for establishing the method in the regular game opera-
impacting car parts. tions, a compound database of both racket covering and booster
In table tennis, the rackets are at the focus of continuous constituents has to be implemented in the future.
development for performance enhancement by the players [2]. The The work was carried out and will be continued e in order to
so-called “speed gluing” with solvent containing glues e which develop a validated tool for control in real competition situation e
significantly influence the performance of the table tennis racket in roughly six steps:
covering e is already banned by the ITTF due to their harmful in-
gredients [3]. However, nowadays so-called “boosters” which are 1. VOC identification and pattern recognition of racket coverings
legally available are occasionally used to improve the performance and boosters using GC-IMS
of the rackets in an irregular way. Those “boosters” mainly contain 2. Refinement of sampling and methodology
softening agents which cause swelling of the covering and changes 3. Database population of relevant compounds
of its properties. Such treatment is also banned - all kind of 4. Database implementation of characteristic pattern of racket
chemicals should only be included to racket coverings under the coverings and boosters
control of the manufactures and their use is controlled by REACH 5. Development of on-site sampling procedure
[4], a guideline on the use of chemicals. In addition, no after 6. Field studies
treatment is allowed that changes the approved properties of the
equipment. During the present feasibility study, we focused on step 1e4.
Control procedures are currently limited to measurements of The development of an appropriate on-site sampling has to be
the covering thickness during competitions as an indirect measure carried out jointly with the International Table Tennis Federation
for irregular treatment. Recently, a hand-held photo ionisation and has to consider the demands of the athletes as well, before field
detector (PID), detecting the total concentration of volatile organic studies can be carried out for validation.
compounds (VOC) and a limit of 3 ppm after a defined sampling is
drafted [5]. Nevertheless, the unspecific detection of the total VOC
concentration is not necessarily a measure for racket covering 2. Experimental setup, material and methods
treatment. Therefore, a more detailed analysis of the racket
covering surface, in the ideal case comprising an identification of 2.1. Table tennis racket coverings
the particular compounds present on the surface would be an
improvement for the control of irregular treatment. But the avail- A competition table tennis racket consists of a blade, made from
ability of suitable, in particular mobile and rapid analytical tools is 85 to 100% wood including a max. 15% other materials. On both
limited. sides of the blade the player or a specialised shop glues a racket
During the present study, we first developed an appropriate covering. After the ban of the use of solvent containing glues by the
sampling in a lab scale and applied it on particular racket coverings ITTF, water based gluing systems are currently being used. During a
as well as on legally available boosters. For the analysis of the VOC competition, a professional player needs to exchange his racket
mixture from the surface of the racket coverings, we used ion coverings regularly, but not the blade. Racket coverings are mainly
mobility spectrometry (IMS) coupled to rapid gas-chromatographic used as a pimple-in-rubber, consisting of a rubber sheet with
pre-separation (GC). The method was already applied for various pimples glued on a sponge. Another type are pimple-out-coverings,
but no problem with after-treatment with softeners occurs with
2
C. Drees, M. Knieb, A. Fechner et al. Analytica Chimica Acta 1154 (2021) 338227

this type. The racket coverings are composed of rubber, which are reduced ion mobility. The combination of GC retention time and ion
produced from various chemicals through a vulcanisation process. mobility enables the identification of the particular compounds and
Technical leaflets can be found under https://www.ittf.com/ the signal intensity is a measure of the concentration. The complex
equipment/ [3]. pattern of VOCs identified and quantified by such analyses enables
Softening agents are used in many rubber products to keep the characterisation of the initial sample. The general procedure of
them smooth, to support extrusion and to adjust particular prop- a GC-IMS analysis from sampling toward sample characterisation is
erties. In table tennis racket coverings, they are used in all modern presented in the scheme of Fig. 1.
offensive pimple-in-products. The manufacturers of racket cover- Initial experiments analysing table tennis racket coverings with
ings integrate softening agents under controlled conditions. The a MCC-IMS (multi-capillary column, MCC, OV-5, Multichrom,
final market product will be authorized by the ITTF and any after Novosibirsk, Russia, for the experimental details, see Ref. [16])
treatment on the authorized product is not allowed. Because at this obtained promising results in differentiation between a booster
stage nobody could control which kind of substances would be and a table tennis racket (see Fig. 2). Nevertheless, unacceptable
used and their influence on the game, or even more important on standard deviations and separation efficiency were observed in this
the health of the user. Only the post-application of softeners causes setup. Therefore, for the present study, a GC-IMS equipped with a
swelling and arching of the covering. Therefore, presently gas chromatographic capillary column (MXT-5, 30 m  0.53 mm x
measuring the covering thickness is the only e but unspecific e 1 mm, Restek GmbH, Bad Homburg, Germany) was applied and the
way to control irregular booster treatment. setup was optimised to a column gas flow of 50 mL/min clean air
For the present study, commercially available racket coverings 5.0 (Linde AG, Dublin, Ireland) and to isothermal conditions at
as used by the world top players were investigated. To investigate 45  C.
all approved coverings [3] was not the objective of this feasibility Those conditions seem unusual for GC operation. But the goal
study. The focus was to demonstrate the potential of the method was to keep the method mobile. Therefore, clean air was used as
described to enable rapid on-site control of the table tennis racket
coverings. Therefore, the coverings investigated will be mentioned
anonymously only, but with the characterisation of their general
content of different concentration and type of softening agents. The
information provided by the producer was available only on the
relative concentration of different softening agents but not on the
particular compounds. Furthermore, no information on the
detailed composition of the coverings was provided. Six different
coverings as mentioned in Table 1 were investigated in the present
study.

2.2. Ion mobility spectrometry coupled to gas chromatography (GC-

IMS)

Ion mobility spectrometry has been primarily developed for the

detection of volatile organic compounds (VOC) but coupling to a GC
pre-separation for the detailed analysis of complex mixtures of
VOCs has only happened in recent years. In general, the gas present
in the ion mobility spectrometer e commonly clean air e is ionised
by b-radiation, resulting in the generation of reactant ions. Intro-
ducing a gas phase sample after GC pre-separation into the ion-
isation region, the compounds of a sample are mainly ionised by
proton transfer in the positive ion mode and by charge transfer in
the negative ion mode. Comprehensive discussions of possible
ionisation processes can be found in the literature [14,15].
Clouds of ions are introduced in the drift region periodically
through a shutter grid and are separated in a weak electric field by
collisions with the molecules of the drift gas counter-flow. As a
consequence, they move with a constant resulting velocity related
to the collision frequency which depends on size and shape of the
ions. Therefore, the ions reach the detector sorted by size and
shape. The inverse of the measured drift time is normalised to drift Fig. 1. Scheme of the entire procedure of GC-IMS analysis from sampling to sample
length, electric field, temperature and pressure, thus obtaining the characterisation.

Table 1
Description of the table tennis racket coverings investigated and the abbreviations used in the following.

Abbreviation Content/relative Concentration

O without softening agents A and/or B

A low concentration of softening agent A
AA medium high concentration of softening agent A
AAA highest concentration of softening agent A
AABB softening agents A and B without information on the concentration compared to the above coverings
AAABBB softening agents A and B in higher concentration than AABB

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C. Drees, M. Knieb, A. Fechner et al. Analytica Chimica Acta 1154 (2021) 338227

Fig. 2. Heatmap of VOCs (signal intensity vs. inverse ion mobility and GC retention time) detected from the headspace MCC-IMS analysis of a booster (A) and of a covering (B). All
booster characteristic signals are indicated (yellow dots with black borders). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web
version of this article.)

carrier gas instead of helium to avoid gas bottles and the column 2.4. Sampling and sample introduction
was operated isothermally to avoid a bulky GC oven. Following van
Deemter, the ideal gas flow rate would have been few mL/min but For sampling the headspace of the coverings, the samples were
with extremely long analysis time under the conditions mentioned incubated as described later on in the method development sec-
before. Therefore, we used a significantly higher flow rate of 50 mL/ tion. A headspace sample of 10 mL was drawn with a glass syringe
min to keep analysis time acceptable. Certainly, those conditions (see Fig. 3 A) and was injected into the sample volume of the GC-
could be matter of optimisation e.g. by using flow ramps instead of IMS (see Fig. 3 B). Subsequently this volume was introduced into
temperature ramps or by using MEMS-based GC columns which the GC column by switching the 6-port valve (Fig. 3 C). The 6-port
would enable the application of temperature ramps [17]. However, valve is controlled by the GC-IMS data acquisition software and the
for the present feasibility study, the GC separation efficiency was time of flushing the sample volume into the GC-column can be
acceptable and provided significantly better results compared to varied. This leads to the different sample volumes mentioned in
the MCC e even under the mentioned suboptimal experimental Table 2 for the 2 different GC setups used in this study.
conditions. For the measurements of the headspace of the coverings with
The general experimental setup of the GC-IMS used here is the PID, the sample inlet of the PID was directly connected to the
described in detail e.g., in Pagonas et al. [6]. The main setup pa- headspace vessel (see Fig. 4) and sampling was carried out for 1 min
rameters for IMS and GC are listed in Table 2. VOCs from a solid by the internal pump of the MiniRae Lite.
sample were analysed using headspace sampling [18].
2.5. Data acquisition, evaluation and visualization

GC-IMS analysis were performed using qIMS software (ISAS,

2.3. Photo ionisation detector Dortmund, Germany). The data were processed, evaluated and
visualised using IONysos software (ION-GAS GmbH, Dortmund,
For comparison, a photo ionisation detector (MiniRae Lite type Germany) and IMSanalysis (ISAS, Dortmund, Germany) in partic-
PGM-7300, Honeywell, Morristown, New Jersey, USA) was applied ular with regard to smoothing, normalisation of signal intensity, ion
as already in use in racket control by the ITTF. The PID MiniRAE Lite mobility and retention time. All particular measurements were
works with an UV-Lamp of 10.6 eV, due to that the PID respond to a repeated 4 times.
wide range of compounds with ionisation potentials below 10.6 eV GC-IMS data are visualised in a so-called heatmap as presented
[19] having a measuring range of 0e5.000 ppm. The general setup exemplarily in Fig. 2 presenting data from MCC-IMS analysis of a
of the instrument is described elsewhere [5]. At present, a booster and a racket covering (AAABBB, see Table 1). The colour
threshold of 3 ppm is defined as a benchmark for MiniRAE Lite coded intensity of the detected VOC signals is presented vs. the
measurements under ambient conditions by the ITTF. inverse ion mobility e which is proportional to the measured drift

Table 2
Experimental setup of the GC-IMS used for the present study.

drift tube length 12 cm

field strength 330 V/cm
grid opening time 300 ms
measuring cycle 100 ms
drift gas flow 150 mL/min clean air 5.0 (Linde AG, Dublin, Ireland)
sample volume 7.28 mL
sample flow 100 mL/min clean air 5.0 (Linde AG, Dublin, Ireland)
GC-column MXT-5; 30 m; 45  C isotherm; column flow 50 mL/min clean air 5.0 (Linde AG, Dublin, Ireland); injected sample volume 8.3 mL

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C. Drees, M. Knieb, A. Fechner et al. Analytica Chimica Acta 1154 (2021) 338227

Fig. 3. Sampling procedure for the headspace measurements of the coverings. A: Sampling from the headspace using a glass syringe. B: Injection of the sample in to the sample
volume of the GC-IMS. C: Introduction of the sample volume into the GC-column by switching of the 6-port valve.

As indicator for the improvement of the sampling method, the

signal volume of the reactant ion peak (RIP) was used. The reactant
ions are generated by the b-radiation ionisation source of the IMS.
The analyte molecules are ionised by charge transfer from the
reactant ions and therefore, their presence is accompanied with a
signal decrease of the RIP signal intensity [14]. Thus, the decrease of
the RIP is an equivalent for the total VOC concentration and
therefore the RIP was used as measure for method optimisation.
The analysis of particular VOC signals was performed to identify
relevant compounds and VOC patterns.

3.1.1. Headspace volume

In the first step, the sample volume was varied using headspace
vials of 25 mL, 140 mL and 340 mL while the sample surface was
adapted accordingly keeping the relation of headspace volume to
sample surface of 5 mL/cm2 (see Fig. 5 A). The decreasing signal
volume of the RIP with increasing headspace volume (see Fig. 5 B)
indicates increasing VOC signals with increasing headspace vol-
ume. This development is linked to increasing sensitivity of the
method.
Fig. 4. Connection of the MiniRae Lite to the headspace vessel.
However, if the reactant ions are mostly consumed, firstly,
quantification is no longer possible and secondly, particular VOC
signals might overload the analyser. Therefore, higher volumes
time (x-axis) e and the GC retention time (y-axis).
were not investigated here. Furthermore, higher volumes would
have been related to extremely large surfaces and consumption of a
3. Results and discussion high amount of sample materials and will not be suitable for the
envisaged field studies. Considering the above results, method
The objective of the present study was first to optimise sampling development was continued with a headspace volume of 340 mL
in order to obtain reproducible and selective quantitative results. and an according sample surface of 68 cm2 which was obtained
After the development of an appropriate sampling method, its with the lowest standard deviation of 2,9%.
potential for accurate detection of irregular treatment of table
tennis coverings should be demonstrated exemplarily. 3.1.2. Headspace incubation temperature
The second optimisation step was the adjustment of the incu-
3.1. Method development bation temperature. It could be observed, that the VOC concen-
tration e again represented by the decreasing RIP e increases with
In order to obtain suitable reproducibility, sampling was opti- increasing temperature (see Fig. 6). The highest VOC concentration
mised systematically inspired by DIN EN 13628e1, part 1 [20] was observed for an incubation temperature 120  C. However, with
describing a standardised method for the determination of residual such a high temperature, a thermal degradation of the sample
solvents in packaging films by headspace analysis. It provides material could be observed, which was related to the appearance of
ranges for the relation of surface to headspace volume, the head- additional signals (see Fig. 7), most probably due to decomposition
space volume itself and the incubation temperature and time. In products and which also could be responsible for the increasing
the following sections, the optimisation steps on those parameters standard deviations. Therefore, an incubation temperature of 85  C
are described in detail while using a sample volume to surface with a good standard deviation of 1.9% was applied for the
relation of 5 mL/cm2. following experiments where visual inspection did not show
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Fig. 5. Three different headspace vials with 25 mL, 140 mL and 240 mL were applied while keeping the relation of headspace volume to sample surface of 5 mL/cm2 (A). The
decreasing RIP signal indicates increasing VOC signals with increasing headspace volume (B).

3.1.3. Incubation time

Finally, the influence of incubation time on the sensitivity was
investigated according to DIN EN 13628e1, part 1 [20]. The samples
were incubated for 15, 20, 30 and 40 min. VOC concentrations rise
significantly even after 15 min while only a slight further increase
after longer incubation is observed (see Fig. 8). Simultaneously the
smallest standard deviation of 1.9% was noticed after 15 min in-
cubation time. After 40 min, sensitivity decreased again. Therefore,
15 min of incubation time was chosen as optimal incubation time,
moreover keeping the total analysis time short.

3.1.4. Method conclusion

The headspace volume of 340 mL was used with a corre-
Fig. 6. Decreasing RIP signal representing increasing VOC concentrations with sponding sample surface of 68 cm2, thus keeping the volume to
increasing incubation temperature. At 120  C, thermal degradation of the sample could surface relation of 5 mL/cm2 on one hand and reducing the con-
be observed (see Fig. 5). sumption of racket coverings. The incubation time of 15 min en-
ables the reduction of the total analysis time while keeping
standard deviations at a minimum e this will compensate with
slightly higher detection limits. The sample was incubated at 85  C,
alteration of the covering. During all measurements, the sampling thus ensuring high sensitivity while avoiding the thermal degra-
syringe was tempered at the adjusted headspace/incubation tem- dation of the covering material. As a consequence, standard de-
perature. For future developments, the identification of compounds viations could be reduced to less than 3% (2.9% at 340 mL sample
observed at elevated temperatures will be subject of more detailed volume, 1.9% at 15 min incubation time and 85  C temperature)
investigations. compared to the 30% obtained before optimisation.

Fig. 7. Incubation temperature of 85  C (A) compared to thermal degradation of the sample at 120  C (B). Additional signals at high temperature most probably are resulting from
pyrolysis.

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covering itself as obviously usually added compound. However, the

concentration increased significantly (>100%) when the booster
was added. Furthermore, 13 signals were found only after the
treatment of the covering, thus enabling an explicit determination
of the irregular treatment of the covering. Only those signals are
indicated in Fig. 9.
Furthermore, an attempt was made to compare the detected
VOC levels to the manufacturer specifications on the relative soft-
ening agent content after production as mentioned in Table 1. As
shown in Fig. 10 for Peak P36 (as indicated in Fig. 9) as an example,
signals could be identified, following in general the manufacturer’s
specifications. In case of P36, this could be a signal related to
softening agent B as the signal appears only in the headspace of the
covering with this softening agent. This demonstrates the selec-
tivity of the method related to the particular compounds used
Fig. 8. Increasing VOC concentrations with increasing incubation time. Standard de- during production.
viations rise with increasing incubation time and after 40 min a sensitivity drop could It is obvious, that the identification of the compounds found as
be observed.
characteristic for the coverings and the bossters respectively is of
interest for the validation of the method. For this purpose, refer-
3.2. Exemplary application ence measurements using thermal desorption GC/MS of samples on
adsorption tools have to be carried out and the results need vali-
After the optimisation of the headspace analysis method using dation by analysis of reference compounds with GC-IMS. However,
GC-IMS as a detector, we exemplarily applied the setup on the due to the non-disclosure agreement with the anonymous provider
available booster and covering samples. Fig. 9 presents the GC-IMS of the coverings investigated here, we are not allowed to publish
data visualised as colour coded heatmap of the analysis of a com- our GC/MS results in this study.
mon covering treated with a booster. The inverse ion mobility e We analysed the headspace of the coverings and the boosters
which is proportional to the measured drift time e on the x-axes investigated here with GC/MS and found several compounds to be
and the GC retention time on the y-axes. It is obvious that the characteristic with this method as well. In particular, we found 17
resolution in the retention time using the 30 m GC column is compounds as characteristic for the coverings e mainly those
significantly higher when compared to another common experi- known from polymerisation and vulcanisation e and 10 as char-
mental setup using a 20 cm MCC column as expected (see Fig. 2 for acteristic for both boosters e mainly softening agents. Furthermore,
comparison). there were at least 3 compounds present in the headspace of the
About 100 particular signals detected from the treated covering coverings and in the boosters as well, substances commonly used
were investigated. Altogether 28 signals were found as character- for treatment of textile materials. Those results are in accordance to
istic for the added booster. 15 of them were also available from the the findings of the GC-IMS analyses.
Finally, we compared our results by GC-IMS headspace analysis
of the available coverings with the results obtained from the
analysis using the MiniRae PID. We did not use the recommended
sampling for the PID but the same sampling procedure as used for
the GC-IMS (see section 2.3 for details). The recommended PID
sampling was optimised for detecting booster application. Here, we
investigated untreated coverings and therefore, relatively low
concentrations could be expected. Furthermore, we intended to
provide comparable conditions to the GC-IMS analysis. Therefore,
the PID results cannot be interpreted in the common way but are

Fig. 9. Heatmap of the GC-IMS signals detected from the headspace analysis of a
common covering after an irregular treatment with booster. The indicated signals (12
yellow dots with black borders) were observed exclusively from the booster. Consid-
ering all signals detected from the booster alone, a 100% increase in total signal in-
tensity after the treatment was observed. Furthermore, the improved selectivity in
retention time compared another common experimental setup using a MCC (see Fig. 2) Fig. 10. Signal intensity of peak P36 (as indicated in Fig. 9) compared to the manu-
is clearly visible. (For interpretation of the references to colour in this figure legend, the facturers specifications on the relative content of the softening agent A and B. P36
reader is referred to the Web version of this article.) seems to be related to softening agent B.

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comparable to the GC-IMS findings in a qualitative way. irregular treatment of table tennis rackets with booster compounds
As we had no information on the specific compounds used as in a first feasibility attempt. It was not designed to provide a
well as on the concentrations, we compared the specifications to comprehensive database of common booster compounds or even
the total VOC concentration detected by GC-IMS which is repre- on all commercially available racket coverings.
sented by the decrease of the reactant ion signal e and not inves- Certainly, the identity of all the detected compounds should be
tigating particular signals. The total VOC level detected by the explored in the future. As it was not possible to receive information
MiniRae PID and the GC-IMS are presented in Fig. 11. It can be on the detailed composition of the racket coverings for obvious
concluded that: reasons, this could be done only through a time-consuming pro-
cedure. Reference samples need to be analysed by GC/MS and the
 Total VOC level does not represent one of the softening agents compounds identified need to be validated with reference sub-
specified by the manufacturer and stances by the GC-IMS again. This for sure will be a prerequisite for
 Except AAABBB, the values of both methods show the similar establishing the method on a regular base during championships
trend but is not necessary to demonstrate the feasibility of detecting
 Standard deviations were found in the range of 6e20% from the booster application in a feasibility study.
PID measurements and less than 1% from the GC-IMS Since the work presented here was a feasibility study, it is
(0.3e0.7%). obvious, that the database of the relevant compounds of coverings
and boosters as well as the VOC pattern database will be subject of
4. Conclusions and outlook continuous extension. In particular, the background VOCs e
released from the water-based glues as well as from the wooden
In order to enable the control of table tennis rackets for irregular core of the racket e must be considered during the interpretation of
treatment with so-called booster, the relevant compounds and the VOC patterns. Furthermore, after the development of a suitable
mixtures from racket coverings and boosters were initially tested on-site sampling e in collaboration with the control organisations
for their detectability using GC-IMS as basis for a database of and professional table tennis players e field studies have to be
relevant compounds. In the following, sampling was optimised in carried out in real tournament situations to validate the method.
accordance with the DIN EN 13628e1, part 1 [20] e describing a Contaminations caused by the athletes as well as external in-
standardised method for the determination of residual solvents in fluences have to be considered in this scenario. Such on-site anal-
packaging films by headspace analysis e with regard to reproduc- ysis, in the ideal case, a non-destructive one, while maintaining the
ibility as well as sensitivity and selectivity. In particular, the ratio of reproducibility and sensitivity, could use the potential of available
headspace volume to the surface as well as the incubation time and in-line pre-concentration systems and mGC columns to improve
temperature were optimised, thus obtaining standard deviations of sensitivity and selectivity. Selectivity in particular has potential for
less than 3% for repeated measurements. improvement, as the experimental conditions of the GC were
It has been be demonstrated, that characteristic VOC patterns suboptimal to keep the method mobile: A high flow rate of 50 mL/
for specified racket coverings as well as for particular boosters min was used to keep analysis time short and the column was
could be identified, thus enabling the identification of approved operated isothermally with clean air as carrier gas to avoid a bulky
coverings as well as irregular treatment with boosters. Further- GC-oven and gas bottles for e.g. helium supply. Furthermore, the
more, the method provides quantitative results as we could sensitivity could even be improved by using the available in-line
demonstrate on behalf of coverings with different booster content, pre-concentration systems [17]. Thus, mobile instrumentation
in this case with standard deviations of at least less than 1%. For a with a total analysis time in the range of few minutes could be
real calibration, such studies need to be carried out with coverings provided [16]. Moreover, automated data evaluation and interpre-
of a known softener content and with systematically boosted tation algorithms have already been implemented.
coverings. Furthermore, quantitative studies have to be performed with
The aim of the present study was to demonstrate the potential regard to establish a tolerance range. This is particularly important
of GC-IMS for a rapid, sensitive and selective on-site control of for table tennis racket manufacturers who use similar softening
agents during the fabrication of the rackets. Moreover, with regard
to legal incontestability, the analyses must be carried out by trained
personnel and will therefore only be used in the short term in
professional sports.
However, despite these great challenges for the acceptance in
competitive sports, GC-IMS has proven its potential to analyse
complex chemical matrices within a very short period of time for
on-site sampling from table tennis rackets and immediate auto-
mated data evaluation and interpretation.

Author contributions

Carolin Drees: Conceptualization, Methodology, Visualization,

Writing. Markus Knieb: Data curation, Formal analysis, Validation,
Visualization. Annika Fechner: Data curation, Formal analysis,
Validation. Joachim Franzke: Methodology, Supervision. Claudia
Herweg: Conceptualization. Wolfgang Vautz: Conceptualization,
Methodology, Supervision, Writing.

Fig. 11. Concentration measured with the MiniRae PID in the headspace as provided
for the GC-IMS analysis compared to the total VOC level observed by GC-IMS. Except
Declaration of competing interest
the covering AAABBB, the values show good agreement but do not represent the
specifications of the provider on softening agents in the samples. The authors declare that they have no known competing
8
C. Drees, M. Knieb, A. Fechner et al. Analytica Chimica Acta 1154 (2021) 338227

financial interests or personal relationships that could have [13] E. Budzyn  ska, S. Sielemann, J. Puton, A.L.R.M. Surminski, Analysis of e-liquids
for electronic cigarettes using GC-IMS/MS with headspace sampling, Talanta
appeared to influence the work reported in this manuscript.
209 (2020) 120594.
[14] G.A. Eiceman, Z. Karpas, H.H. Hill, Ion Mobility Spectrometry, Taylor & Francis,
Acknowledgements Boca Raton, FL, USA, 2013.
[15] H. Borsdorf, G.A. Eiceman, Ion mobility spectrometry: principles and appli-
cations, Appl. Spectrosc. Rev. 41 (4) (2006) 323e375.
The financial support of the Ministerium für Kultur und Wis- [16] W. Vautz, J. Franzke, S. Zampolli, I. Elmi, S. Liedtke, On the potential of ion
senschaft des Landes Nordrhein-Westfalen and der Regierende mobility spectrometry coupled to GC pre-separation - a tutorial, Anal. Chim.
Bürgermeister von Berlin, Senatskanzlei Wissenschaft und For- Acta 1024 (2018) 52e64.
[17] S. Liedtke, S. Zampolli, I. Elmi, L. Masini, T. Barboza, E. Dalcanale, R. Pinalli,
schung is acknowledged gratefully. Furthermore, the establishment M. Pa€hler, C. Drees, W. Vautz, Hyphenation of a MEMS based pre-concentrator
of contacts to the ITTF by our table tennis playing PhD student and GC-IMS, Talanta 191 (2018) 141e148.
Pascal Vogel is appreciated. Last but not least we want to thank [18] M.J. Sithersingh, N.H. Snow, Headspace-gas chromatography, in: Colin Poole
(Ed.), Gas Chromatography, Elsevier, 2012.
Michael Schilling, ISAS Dortmund, for helping us with his chemical [19] M.L. Langhorst, Photoionization detector sensitivity of organic compounds,
expertise and Chandrasekhara Hariharan for proof reading as a J. Chromatogr. Sci. 19 (2) (1981) 98e103.
native English speaker. [20] DIN EN 13628-1:2003-01 „Verpackung; Flexible Packstoffe e Bestimmung der
Restlo€ semittel durch statische Dampfraumanalyse mittels Gaschromatogra-
phie - Teil 1: Absolute Verfahren“.
Abbreviations

GC gas chromatography Carolin Drees received her M. Sc. in Applied Biomedical Engineering from the Hamm-
Lippstadt University of Applied Science, Germany, focusing on the development of a
IMS ion mobility spectrometry non-radioactive plasma ionisation source for ion mobility spectrometry. Since 2017,
ITTF International Table Tennis Federation she is working at ISAS to obtain her Ph. D. degree with a center on applications and
MS mass spectrometry developments in ion mobility spectrometry.

PID photo ionisation detector

RIP reactant ion peak Markus Knieb: After graduating from school in 2012, I started studying chemistry at
UV ultra-violet light Heidelberg University. In 2016 I transferred to the Hamm-Lippstadt University to study
environmental monitoring and forensic chemistry. I finished my studies in environ-
VOC volatile organic compounds
mental monitoring and received the title Bachelor of Engineering in 2020. Currently
I am doing the consecutive master’s degree in the field of environment and hazardous
References substance analysis at the Hamm-Lippstadt University.

[1] R. Pielke, E. Boye, Scientific integrity and anti-doping regulation, International

Journal of Sport Policy and Politics 11 (2) (2019) 295e313. Annika Fechner finished her M. Sc in Environmental and hazardous substance anal-
[2] Y. Tsuji, K. Kimura, Effects of booster on bounce properties of rubber (Data for ysis at the Hamm-Lippstadt University of Applied Science, Germany focusing on the
proposal of banning post-treatment of rubbers). International Journal of liquid sample introduction for ion mobility spectrometry in August 2020. Since then
Table Tennis Sciences No. 8, in: The 13th ITTF Sports Science Congress May she is working at ISAS to obtain her Ph. D. degree
11-12, 2013, Paris, France, 2013, pp. 62e67.
[3] Ittf 2020: website on table tennis equipment. https://www.ittf.com/
equipment. Joachim Franzke received his PhD in applied plasma spectrometry in 1994 from TU
[4] REACH, Commission Regulation (EU) 2020/878 of 18 June 2020 Amending Dortmund. He held positions at the National Institute of Standards and Technology
Annex II to Regulation (EC) No 1907/2006 of the European Parliament and of (NIST), Boulder, CO in the group of Leo Hollberg and University of Hohenheim, Ger-
the Council Concerning the Registration, Evaluation, Authorisation and Re- many. Currently, he is head of the miniaturization group at ISAS and teacher at the TU
striction of Chemicals (REACH), 2020. https://eur-lex.europa.eu/eli/reg/2020/ Dortmund. His main research interest is the development of analytical methods for the
878/oj. miniaturization of analytical devices, especially the development and characterisation
[5] H. Hori, S. Ishimatsu, Y. Fueta, M. Hinoue, T. Ishidao, Comparison of sensor of new ionisation sources.
characteristics of three real-time monitors for organic vapors, J. Occup. Health
57 (2014), https://doi.org/10.1539/joh.14-0146-OA.
[6] N. Pagonas, W. Vautz, L. Seifert, R. Slodzinski, J. Jankowski, W. Zidek, Claudia Herweg: After studying sports and an education in foreign trade started to
T.H. Westhoff, Volatile organic compounds in uremia, PloS One 7 (9) (2012), work for one of the leading table tennis brands DONIC. Changed to a table tennis shop
e46258. 1000 & 1 HOLZ for one year. Followed by 20 years in a leading table tennis racket
[7] M. Westhoff, P. Litterst, L. Freitag, W. Urfer, S. Bader, J.I. Baumbach, Ion covering producer as a managing director and shareholder. A period of 6 years as a self
mobility spectrometry for the detection of volatile organic compounds in employed consultant of table tennis companies followed. Since 2018 full time
exhaled breath of patients with lung cancer: results of a pilot study, Thorax 64 employed as the Head of Equipment inside the International Table Tennis Federation.
(2009) 744e748.
[8] W. Vautz, C. Hariharan, O. Kayser, Fast detection of recent cannabis sativa L.
Consumption in exhaled breath using a mobile ion mobility spectrometer, Wolfgang Vautz: After studies in physics, informatics and meteorology research work
Journal for Forensic Research and Crime Science 2019 (3) (2019) 1e11. on atmospheric trace compounds and particulate matter and on modelling of areal
[9] C. Drees, W. Vautz, S. Liedtke, C. Rosin, K. Althoff, M. Lippmann, concentration distributions. PhD finished at Johannes-Gutenberg-University Mainz,
S. Zimmermann, T. Legler, D. Yildiz, T. Perl, N. Kunze-Szikszay, GC-IMS Germany in 1991 followed by research in the atmospheric chemistry department of
headspace analyses allow early recognition of bacterial growth and rapid ISAAS, Dortmund in a German-Brazilian project on Vegetation damage in the Atlantic
pathogen differentiation in standard blood cultures, Appl. Microbiol. Bio- rain forest including measurement of air pollution, modelling of emission, distribution,
technol. 103 (2019) 9091e9101. deposition and effects. Since 2002 involved in the ion mobility spectrometry group
[10] C. Tiebe, H. Miessner, B. Koch, T. Hübert, Detection of microbial volatile focused on method development and application for process control, food quality
organic compounds (MVOCs) by ion-mobility spectrometry, Anal. Bioanal. and safety as well as medical diagnosis and therapy control via breath analysis in
Chem. 395 (2009) 2313e2323. the frame of the department of miniaturization. Since 2014 in part time CEO of ION-
[11] W. Vautz, J.I. Baumbach, Analysis of bio-processes using ion mobility spec- GAS GmbH, a joint spin-off company of ISAS and TU Dortmund. The company is
trometry, Eng. Life Sci. 8 (2008) 19e25. focused on feasibility studies, method development and on tailor-made hardware
[12] W. Vautz, D. Zimmermann, M. Hartmann, J.I. Baumbach, J. Nolte, J. Jung, Ion based on GC e ion mobility spectrometry.
mobility spectrometry for food quality and safety, Food Addit. Contam. 23 (11)
(2006) 1064e1073.