Technical
Applications
• Page 238
Applications of desorption corona beam
ionization-mass spectrometry
• Page 243
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
• Page 249
Analysis of styrene leached from polystyrene
cups using GCMS coupled with Headspace (HS)
sampler
PO-CON1474E
Applications of Desorption Corona
Beam Ionization-Mass Spectrometry
ASMS 2014
WP 393
Yuki Hashi1, Shin-ichi Kawano1, Changkun Li1, Qian Sun1,
Taohong Huang1, Tomoomi Hoshi2, Wenjian Sun3
Shimadzu (China) Co., Ltd., Shanghai, China
2
Shimadzu Corporation, Kyoto, Japan
3
Shimadzu Research Laboratory (Shanghai) Co., Ltd.,
Shanghai, China
1
Applications of Desorption Corona Beam
Ionization-Mass Spectrometry
Introduction
Numerous ambient ionization mass spectrometric
techniques have been developed for high throughput
analysis of various compounds with minimum sample
pretreatment.(1) Desorption corona beam ionization (DCBI)
is a more recent technique.(2) In DCBI, helium is used as
discharge gas and heating of the gas is required for sample
desorption. A visible thin corona beam is formed by using
hollow needle/ring electrode structure. This feature
facilitates localizing sampling areas and obtaining good
reproducibility of data. Details of DCBI hardware are
shown in Figs. 1 and 2. In this study, DCBI was applied for
analysis of various samples.
Helium flow
HVDC
-
Heated thin
wall tubing
+
LVDC
Discharge
needle
Counter
electrode
Sampling
capillary
MS inlet
Sample and stage
Figure 1 Schematic diagram of DCBI
DCBI probe
Corona beam
MS Inlet
Manual liquid
sampler
Figure 2 DCBI interface
2
Applications of Desorption Corona Beam
Ionization-Mass Spectrometry
Method
Sample Preparation
Samples (melamine, saturated hydrocarbon mixture, polyaromatic hydrocarbon mixture, testosterone, pirimicarb, and
methomyl) were dissolved in methanol or acetonitrile.
DCBI-MS Analysis
Samples were analyzed using a DCBI system coupled to a LCMS-2020 quadrupole mass spectrometer (Shimadzu
Corporation, Japan). The system was operated with the DCBI control software and LabSolutions for LCMS version 5.42.
Analytical Conditions
DCBI
Flow rate
HV discharge
He gas temperature
Sample volume
:
:
:
:
0.6 L/min
+2.0-3.0 kV
350 ºC
1, or 2 µL
MS (LCMS-2020 quadrupole mass spectrometer)
Polarity
DL temperature
BH temperature
Mass range
:
:
:
:
Positive
250 ºC
400 ºC
m/z 100-500
Results and Discussion
In this experiment, all compounds with variety of polarity
from non- to high-polar gave protonated molecules (Figs.
3-8). Methomyl gave also fragment ions (m/z 106) by
cleavage at methylcarbamoyl group, while fragment ions
with significant intensity were not observed for other
compounds. Analysis time was less than 1 minute.
Inten. (x1,000)
127.1
2.25
2.00
1.75
1.50
1.25
1.00
0.75
0.50
0.25
0.00
136.0
100.0
105.0
110.0
115.0
120.0
125.0
130.0
135.0
148.6
140.0
145.0
m/z
Figure 3 Mass spectrum of melamine (0.5 mg/mL)
3
Applications of Desorption Corona Beam
Ionization-Mass Spectrometry
Inten. (x100,000)
1.50
213.2
1.25
241.3
255.3
269.3
199.2
1.00
283.3
297.3
185.2
0.75
311.3
0.50
171.2
325.3
0.25
339.3
157.2
115.1 143.2
0.00
100
367.4
150
200
250
300
350
Compound
C 10H 22
C 11H 24
C 12H 26
C 13H 28
C 14H 30
C 15H 32
C 16H 34
C 17H 36
C 18H 38
C 19H 40
C 20H 42
C 21H 44
C 22H 46
C 23H 48
C 24H 50
C 25H 52
MW
142
156
170
184
198
212
226
240
254
268
282
296
310
324
338
352
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Anthracene
Phenanthrene
Pyrene
Fluoranthene
Chrysene
Benzo[a]anthracene
MW
128
152
154
166
178
178
202
202
228
228
m/z
Figure 4 Mass spectrum of saturated hydrocarbon mixture (1 mg/mL)
6.5
Inten. (x10,000)
153.1
6.0
5.5
155.2
5.0
4.5
179.1
4.0
3.5
3.0
2.5
167.2
2.0
1.5
1.0
0.5
0.0
100.0
209.1
195.1
129.1
141.2
115.1
125.0
150.0
203.1
235.1
175.0
200.0
225.0
276.2
250.0
275.0
m/z
Figure 5 Mass spectrum of polyaromatic hydrocarbon mixture (2 mg/mL)
Inten. (x10,000)
289.2
7.0
6.0
5.0
4.0
3.0
2.0
1.0
0.0
112.1
331.2
150
200
250
300
350
424.5 461.4
400
450
m/z
Figure 6 Mass spectrum of testosterone (1 mg/mL)
4
Applications of Desorption Corona Beam
Ionization-Mass Spectrometry
Inten. (x100,000)
Inten. (x100,000)
239.2
9.0
163.0
1.2
1.1
8.0
105.9
1.0
7.0
0.9
6.0
0.8
0.7
5.0
0.6
4.0
0.5
3.0
0.4
0.3
2.0
0.2
1.0
0.0
100
182.2
150
200
0.1
250
300
350
400
450
Figure 7 Mass spectrum of pirimicarb (0.5 mg/mL)
m/z
194.0
121.9
0.0
100
208.0
150
252.0
200
250
354.1 394.3
300
350
400
450
m/z
Figure 8 Mass spectrum of methomyl (0.5 mg/mL)
Conclusion
The DCBI system was successfully applied for analysis of samples with various polarity.
Mass spectra were quickly obtained after sample introduction to the DCBI probe.
The method is useful for fast identification of various compounds.
References
(1) Monge ME et al, Chem. Rev. 113 (2013), 2269-2308
(2) Hua W et al, Analyst 135 (2010), 688-695
First Edition: June, 2014
www.shimadzu.com/an/
For Research Use Only. Not for use in diagnostic procedures.
The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.
The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
to change without notice.
© Shimadzu Corporation, 2014
PO-CON1456E
Rapid analysis of carbon fiber
reinforced plastic using DART-MS
ASMS 2014
TP 782
Hideaki Kusano1, Jun Watanabe1, Yuki Kudo2,
Teruhisa Shiota3
1 Shimadzu Corporation, Nakagyo-ku, Kyoto, Japan;
2 Bio Chromato, Inc., Fujisawa, Japan;
3 AMR Inc., Meguro-ku, Tokyo, Japan
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
Introduction
DART (Direct Analysis in Real Time) can ionize and analyze
samples directly under atmospheric pressure, independent
of the sample forms. Then it is also possible to measure in
form as it is, without sample preparation. Qualitative
analysis of target compounds can be conducted very fast
and easily by combining DART with LCMS-2020/8030
which have ultra high-speed scanning and ultra high-speed
polarity switching.
Carbon-fiber-reinforced plastics, CFRP is the
fiber-reinforced plastic which used carbon fiber for the
reinforced material, which is only called carbon resin or
carbon in many cases. An epoxy resin is mainly used for a
base material in CFRP. While CFRP is widely used taking
advantage of strength and lightness, most approaches
which measure CFRP with analytical instruments were not
tried, triggered by the difficulty of the preparation.
DART (Direct Analysis in Real Time), a direct atmospheric
pressure ionization source, is capable of analyzing samples
with little or no sample preparation. Here, rapid analysis of
carbon fiber reinforced plastic was carried out using DART
combined with a mass spectrometer.
Figure 1 CFRP：carbon-fiber-reinforced plastic
Methods and Materials
Thermosetting polyimide (carbon-fiber-reinforced plastics)
and thermoplastic polyimide (control sample) were
privately manufactured. After cutting a sample in a suitable
size, it applied DART-MS analysis. They were introduced to
the DART gas using tweezers. The DART-OS ion source
(IonSense, MA, USA) was interfaced onto the single
quadrupole mass spectrometer LCMS-8030 (Shimadzu,
Kyoto Japan). Ultra-fast polarity switching was utilized on
the mass spectrometer to collect full scan data.
LCMS-8030 can achieve the polarity switching time of
15msec and the scanning speed of up to 15,000u/sec,
therefore the loop time can be set at less than 1 second
despite the relatively large scanning range of 50-1,000u.
MS condition (LCMS-8030; Shimadzu Corporation)
Ionization
: DART (Direct Analysis in Real Time)
2
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
High Speed Mass Spectrometer
UFswitching
High-Speed Polarity Switching 15msec
UFscanning
High-Speed Scanning 15,000u/sec
Figure 2 DART-OS ion source (IonSense) & triple quadrupole LCMS (Shimadzu)
Result
3 CFRP samples were analyzed by DART-MS. Mass chromatograms of each sample were shown in Figure 3 and mass
spectra in Figure 4.
Sample
#1 thermoplastic polyimide (control)
#2 thermosetting polyimide (molded; dried)
#3 thermosetting polyimide (immediately after molded; wet state with solvent)
Analytical Condition
Heater Temperature (DART) : 300ºC
Measuring mode (MS)
: Positive/Negative scanning simultaneously
1:MIC1(+)
Positive TIC m/z 50-500
50000000
25000000
0
6000000
5000000
2:MIC1(-)
Negative TIC m/z 50-500
4000000
3000000
2000000
1000000
#1
0
7.5
8.0
8.5
9.0
#2
9.5
10.0
10.5
#3
11.0
11.5
12.0
min
Figure 3 TIC chromatogram of CFRP samples #1, #2, #3
3
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
Inten.
7.5
(x1,000,000)
Positive, m/z 50-300
#1
5.0
2.5
0.0
100.1
50
Inten.
7.5
172.1
100
282.2
228.3
200
250
m/z
(x1,000,000)
#2
2.5
Positive, m/z 50-300
N-methyl pyrrolidone
C5H9NO
Mw 99
5.0
[M+H]+
[2M+H]+
199.1
100.1
0.0
199.1
150
172.2
50
100
150
282.3
200
250
m/z
Inten. (x1,000,000)
7.5
100.1
199.1
Positive, m/z 50-300
#3
5.0
2.5
0.0
50
100
150
200
250
m/z
Figure 4 DART-MS spectra of each sample
Since the thermosetting polyimide used for this
measurement was molded using the organic solvent
(N-methyl pyrrolidone, C5H9NO, molecular weight 99),
molecular related ions of N-methyl pyrrolidone, [M+H]+
(m/z 100) and [2M+H]+ (m/z 199), were detected very
strongly in the mass spectrum of #1. The mass spectrum
of #2 also showed the same ions that intensity was
intentionally detected strongly compared with #3
although intensity was weak compared with #1. Even if
it raised the heating gas temperature of DART to high
temperature (up to 500°C), MS signal considered to
originate in the structural information of CFRP was not
able to be obtained.
Then, the optional heating mechanism, ionRocket (Bio
Chromato, Inc.; Figure 5), in which a sample could be
heated directly was developed to the sample stage of
DART, and analysis of CFRP was verified by heating the
sample directly up to 600°C.
Sample
#4 thermosetting polyimide (molded; dried)
#5 thermoplastic polyimide (control)
Analytical Condition
Heater Temperature (DART)
: 400°C
Temperature control (ionRocket) : 0-1min room temp., 4min 600°C
Measuring mode (MS)
: Positive scanning
4
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
600°C
r.t.
1
4
time[min]
evaporated ingredient
excitation helium
MS
spectrometer
DART ion source
sample pot
small heating furnace
heater
Figure 5 DART-MS system integrated with ionRocket
When heating temperature was set to 600ºC, the rudder
shape signals of 28u (C2H4) interval was appeared
around m/z 900. This signal was more notably detected
with the thermosetting polyimide sample than the
thermoplastic sample. Since the sample was heated at
high temperature, it was considered that the thermal
decomposition of resin started, the thermal
decomposition ingredient of polyimide clustered, and
possibly the structures of the rudder signals of equal
interval were generated.
5
Rapid analysis of carbon fiber reinforced plastic
using DART-MS
#4
Zoom
#5
#4
thermosetting polyimide
#5
thermoplastic polyimide
Figure 6 DART-MS with ionRocket spectra of each sample
Conclusions
The result of having analyzed the carbon fiber plastic CFRP (thermosetting polyimide and thermoplastic polyimide)
using DART-MS,
a. residue of the solvent used in fabrication was able to be checked by direct analysis of CFRP by DART.
b. analyzing CFRP by DART and the heating option ionRocket, the difference between thermosetting polyimide and
thermoplastic polyimide was able to be found out.
Acknowledgment
We are deeply grateful to Mr. Yuichi Ishida, Japan Aerospace Exploration Agency (JAXA), offered the CFRP sample
used for this experiment.
First Edition: June, 2014
www.shimadzu.com/an/
For Research Use Only. Not for use in diagnostic procedures.
The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.
The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
to change without notice.
© Shimadzu Corporation, 2014
PO-CON1464E
Analysis of styrene leached from
polystyrene cups using GCMS coupled
with Headspace (HS) sampler
ASMS 2014
TP763
Ankush Bhone(1), Dheeraj Handique(1), Prashant Hase(1),
Sanket Chiplunkar(1), Durvesh Sawant(1), Ajit Datar(1),
Jitendra Kelkar(1), Pratap Rasam(1), Nivedita Subhedar(2)
(1) Shimadzu Analytical (India) Pvt. Ltd., 1 A/B Rushabh
Chambers, Makwana Road, Marol, Andheri (E),
Mumbai-400059, Maharashtra, India.
(2) Ramnarain Ruia College, L. Nappo Road,
Matunga (E), Mumbai-400019, Maharashtra, India.
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
Introduction
Worldwide studies have revealed the negative impacts of
household disposable polystyrene cups (Figure 1) on
human health and environment.
Molecular structure of styrene is shown in Figure 2. Styrene
is considered as a possible human carcinogen by the WHO
and International Agency for Research on Cancer (IARC).[1]
Migration of styrene from polystyrene cups containing
beverages has been observed.[2] Styrene enters into our
body through the food we take, mimics estrogens in the
body and can therefore disrupt normal hormonal
functions. This could also lead to breast and prostate
cancer.
The objective of this study is to develop a sensitive,
selective, accurate and reliable method for styrene
determination using low carryover headspace sampler,
HS-20 coupled with Ultra Fast Scan Speed 20,000 u/sec,
GCMS-QP2010 Ultra to assess the risk involved in using
polystyrene cups.
Figure 1. Polystyrene cup
Figure 2. Structure of styrene
Method of Analysis
Extraction of styrene from polystyrene cups
This study was carried out by extracting styrene from commercially available polystyrene cups and recoveries were
established by spiking polystyrene cups with standard solution of styrene. Solutions were prepared as follows,
1) Standard Stock Solution:
1000 ppm of styrene standard stock solution in DMF: Water-50:50 (v/v) was prepared. It was further diluted with
water to make 100 ppm and 1 ppm of standard styrene solutions.
2) Calibration Curve:
Calibration curve was plotted using standard styrene solutions in the concentration range of 1 to 50 ppb with water as
a diluent. 5 mL of each standard styrene solution was transferred in separate 20 mL headspace vials and crimped with
automated crimper.
3) Sample Preparation:
150 mL of boiling water (around 100 ºC)[1] was poured into polystyrene cups. The cup was covered with aluminium foil
and kept at room temperature for 1 hour. After an hour, 5 mL of sample from the cup was transferred into the 20 mL
headspace vial and crimped with automated crimper.
Method was partly validated to support the findings by performing reproducibility, linearity, LOD, LOQ and recovery
studies. For validation, solutions of different concentrations were prepared using standard stock solution of styrene (1000
ppm) as mentioned in Table 1.
2
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
Table 1. Method validation parameters
Parameter
Concentration (ppb)
Linearity
1, 2.5, 5, 10, 20, 50
Accuracy / Recovery
2.5, 10, 50
Precision at LOQ level
1
Reproducibility
50
HS-GCMS Analytical Conditions
Figure 3 shows the analytical instrument, HS-20 coupled with GCMS-QP2010 Ultra on which samples were analyzed with
following instrument parameter.
Figure 3. HS-20 coupled with GCMS-QP2010 Ultra by Shimadzu
HS-GCMS analytical parameters
Headspace parameters
• Sampling Mode
• Oven Temp.
• Sample Line Temp.
• Transfer Line Temp.
• Equilibrating Time
• Pressurizing Time
• Pressure Equilib. Time
• Load Time
• Load Equilib. Time
• Injection Time
• Needle Flush Time
• GC Cycle Time
:
:
:
:
:
:
:
:
:
:
:
:
Loop
80.0 ºC
130.0 ºC
140.0 ºC
20.00 min
0.50 min
0.10 min
0.50 min
0.10 min
1.00 min
10.00 min
23.00 min
3
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
Chromatographic parameters
• Column
• Injection Mode
• Split Ratio
• Carrier Gas
• Flow Control Mode
• Linear Velocity
• Pressure
• Column Flow
• Total Flow
• Total Program Time
• Column Oven Temp.
:
:
:
:
:
:
:
:
:
:
:
Rxi-5Sil MS (30 m L x 0.25 mm I.D., 0.25 μm)
Split
10.0
Helium
Linear Velocity
36.3 cm/sec
53.5 kPa
1.00 mL/min
14.0 mL/min
12.42 min
Rate (ºC /min)
Temperature (ºC)
50.0
40.00
200.0
30.00
280.0
Hold time (min)
0.00
1.00
5.00
Mass Spectrometry parameters
• Ion Source Temp.
• Interface Temp.
• Ionization Mode
• Event Time
• Mode
• m/z
• Start Time
• End Time
:
:
:
:
:
:
:
:
200 ºC
230 ºC
EI
0.20 sec
SIM
104,103 and 78
1.00 min
5.00 min
Results
Fragmentation of styrene
Mass spectrum of styrene is shown in Figure 4. From the
mass spectrum, base peak of m/z 104 was used for
quantitation where as m/z 103 and 78 were used as
reference ions.
SIM chromatogram of 50 ppb standard styrene solution
with m/z 104, 103 and 78 is shown in Figure 5.
Method validation data is summarized in Table 2. Figures 6
and 7 show overlay of SIM chromatograms for m/z 104 at
linearity levels and calibration curve respectively.
4
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
Inten.
104
100
75
50
103
78
25
51
44
52
63
58
0
45.0
50.0
55.0
60.0
74
65
65.0
70.0
75.0
85
80.0
85.0
89
90.0
98
95.0
100.0
105.0 m/z
Figure 4. Mass spectrum of styrene
(x1,000,000)
104.00 (10.00)
7.5 103.00 (10.00)
78.00 (10.00)
5.0
2.5
0.0
2.325
2.350
2.375
2.400
2.425
2.450
2.475
2.500
2.525
min
Figure 5. SIM chromatogram of 50 ppb standard styrene solution
Summary of validation results
Table 2. Validation summary
Sr. No.
Compound Name
Parameter
Concentration in ppb
Result
1
Reproducibility (% RSD)
50
% RSD : 1.74 (n=6)
2
Linearity* (R2)
1 – 50
R2 : 0.9996
3
4
5
LOD
Styrene
LOQ
Precision at LOQ
1 – 50
1
LOD : 0.2 ppb
LOQ : 1 ppb
S/N ratio : 38 (n=6)
% RSD : 3.2 (n=6)
* Linearity levels – 1, 2.5, 5, 10, 20 and 50 ppb.
5
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
(x1,000,000)
2.00
Area
m/z : 104.00
1.75
1250000
50 ppb
1.50
R2 = 0.9996
1000000
20 ppb
1.25
10 ppb
1.00
5 ppb
0.75
2.5 ppb
0.50
1 ppb
750000
500000
250000
0.25
0.00
0
2.2
2.3
2.4
2.5
2.6
0
min
10
Figure 6. Overlay of SIM chromatograms for m/z 104 at linearity levels
20
30
40
Conc.
Figure 7. Calibration curve for Styrene
Quantitation of styrene in polystyrene cup sample
Analysis of leachable styrene from polystyrene cups was
done as per method described earlier. Recovery studies
were carried out by spiking 2.5, 10 and 50 ppb of standard
styrene solutions in polystyrene cups. Figure 8 shows
overlay SIM chromatogram of spiked and unspiked
samples. Table 3 shows the summary of results.
(x100,000)
m/z : 104.00
7.5
5.0
Spiked
2.5
Unspiked
0.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
min
Figure 8. Overlay SIM chromatograms of spiked and unspiked samples
Table 3. Summary of results for sample analysis
Sr. No.
Sample Name
Parameter
1
Unspiked sample
Precision
2
Spiked polystyrene cups
Recovery
Observed
Concentration
in ppb
Spiked
Concentration
in ppb
% Recovery
9.8
NA
NA
12.0
2.5
88.0
18.5
10
87.0
55.9
50
92.2
6
Analysis of styrene leached from polystyrene cups
using GCMS coupled with Headspace (HS) sampler
Conclusion
• HS-GCMS method was developed for quantitation of styrene leached from polystyrene cup. Part method validation was
performed. Results obtained for reproducibility, linearity, LOQ and recovery studies were within acceptable criteria.
• With low carryover, the characteristic feature of HS-20 headspace, reproducibility even at very low concentration level
could be achieved easily.
• Ultra Fast Scan Speed 20,000 u/sec is the characteristic feature of GCMS-QP2010 Ultra mass spectrometer, useful for
quantitation of styrene at very low level (ppb level) with high sensitivity.
References
[1] Maqbool Ahmad, Ahmad S. Bajahlan, Journal of Environmental Sciences, Volume 19, (2007), 422, 424.
[2] M. S. Tawfika; A. Huyghebaerta, Journal of Food Additives and Contaminants, Volume 15, (1998), 595.
First Edition: June, 2014
www.shimadzu.com/an/
For Research Use Only. Not for use in diagnostic procedures.
The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu.
The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its
accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the
use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject
to change without notice.
© Shimadzu Corporation, 2014