No.

SSI-GCMS-1504

Gas Chromatograph Mass Spectrometer

A Pyrolysis-GC/MS Screening System for

Analysis of Phthalate Esters and
No. GCMS-1504 Brominated Flame Retardants
■ Introduction ranges, releasing the PBBs, PBDEs and phthalate
The Restriction of Hazardous Substances (RoHS) esters from the polymer matrix for subsequent
Directive controls six hazardous substances commonly analysis by GC/MS.
used in electronic and electrical equipment (1). Two of
the restricted substances are compound classes In this application note, a PY-GC/MS method has
commonly used in flame retardants: polybrominated been used to screen for seven phthalate esters and
biphenyls (PBB) and polybrominated diphenyl ethers 11 brominated flame retardants. A commercially
(PBDE), both known to cause serious health concerns available method package was used, which includes
due to their high halogen content. Beside brominated phthalate ester and PBDE standards, pre-registered
flame retardants, phthalate esters have also been instrument methods with acquisition and data
controlled by a number of regulatory authorities. The processing parameters, and calibration curves for
United States congress has prohibited the use of six semi-quantitative calculation of compound
specified phthalate esters (DBP, DEHP, BBP, DINP, concentration. Quantitation results were generated
DIDP and DnOP) in children’s toys at concentrations with minimal sample preparation, requiring no
higher than 0.1% under the Consumer Product Safety organic solvents. A software program for efficient
Improvement Act of 2008 (CPSIA) (2). The European multi-analyte data confirmation and QAQC review is
commission has identified DBP, DEHP and BBP as also discussed.
reproductive toxicants under directive 2005/84/EC (3).
The Environmental Protection Agency (EPA) has ■ Experimental
proposed adding eight phthalates to the list of
chemicals of concern under the Toxic Substances Py-Screener Package
Control Act (TSCA), including DIBP, DBP, BBP, DEHP, This study was conducted using the Shimadzu
DnOP, DINP, DnPP and DIDP (4). The Food and Drug GCMS-QP2010 Ultra, Frontier Multi-Shot EGA/PY-
Administration (FDA) Center for Drug Evaluation and 3030D pyrolyzer, and AS-1020E Auto-Shot sampler,
Research (CDER) recommends avoiding the use of as shown in Figure 1.
DBP and DEHP as excipients in CDER-regulated drug
and biologic products, including prescription and
nonprescription products (5).

To quantitate these substances in a polymer matrix,

the traditional approach involves solvent extraction
of PBBs, PBDEs and phthalate esters from the sample
matrix, followed by detection and quantitation by
gas chromatography/mass spectrometry (GC/MS).
This method is time consuming and poses the risk of
exposure to multiple toxic solvents.

Pyrolysis followed by GC/MS has been well

established for detection of volatile and semi-volatile
compounds in both natural and synthetic polymers.
Using the pyrolysis technique described here, a
temperature programed micro-furnace provides
Figure 1: Frontier Multi-Shot EGA/PY-3030D pyrolyzer and AS-1020E
thermal desorption processes at two temperature Auto-Shot sampler installed on the Shimadzu GCMS-QP2010 Ultra
 No. SSI-GCMS-1504

The Frontier Multi-Shot EGA/PY-3030D pyrolyzer and Analytical standards used for this project were
AS-1020E Auto-Shot sampler were installed on the included with the Py-Screener package. The
Shimadzu GCMS-QP2010 Ultra, with a UA-PBDE phthalate standards were comprised of three thin
metal capillary column (15 m x 0.25 mm x 0.05 µm). polymer films, which contain seven phthalates at 0,
A method package called Py-Screener has been 100 ppm, and 1000 ppm, and one flame retardant
developed and applied in this application. Py- standard containing 11 PBBs and PBDEs. All
Screener is a method package targeting seven standards and samples were prepared by slicing off
phthalates and 11 brominated flame retardants. It small pieces of the polymer using the knife from the
contains pre-registered instrument acquisition sampling tool kit. Approximately 0.5 mg of standards
methods for the Pyrolyzer and the GC/MS, as well as and samples were weighed using an electronic
a data processing analysis method including balance with accuracy of 0.01 mg before loading
quantitation parameters and calibration curves into the sample cups. For ease of the application, the
developed using phthalate and PBDE standards. Py-Screener package also includes sample
Refer to Table 1 and Table 2 for experimental details preparation videos, illustrated troubleshooting
and complete compound list. procedures and routine maintenance.

Table 1: Experimental conditions for the instrument acquisition method

Gas Chromatograph CG-2010 Plus
Column UA-PBDE, 15 m x 0.25 mm x 0.05 µm (Shimadzu PN 220-94824-20)
80 °C, no hold
Oven Program
20 °C/minute to 300 °C, hold 5 minutes
Split mode, split ratio 50:1
Injector 300 °C
Split Liner w/ wool (Shimadzu PN 220-90784-00)
Carrier Gas Helium
Carrier Gas Flow Constant linear velocity mode, 52.1 cm/second
Total Flow 54 mL/minute, Column Flow = 1.00 mL/minute
Purge Flow 3.0 mL/minute
Interface Temperature 320 °C
Mass Spectrometer GCMS-QP2010 Ultra
Ion Source Temperature 230 °C
Solvent Cut Time 0.5 minutes
Detector Voltage Relative to tune + 0.1 kV
Acquisition mode: Scan/SIM
Total loop time 0.45 second
MS Operating Mode
Scan event time 0.15 second SIM event time 0.3 second
Mass range: 50-1000 amu SIM method details listed in table 2
Pyrolyzer PY-3030D (Frontier Labs)
Sample amount 0.5 mg
Furnace Temp TD1 200 °C to 300 °C @ 20 °C/minute, total 5 minutes
TD2 300 °C to 340 °C @ 5 °C/minute, total 9 minutes
PY-GC Interface Temperature Furnace temperature plus 100 °C, up to 300 °C
Analysis Time
PY program 14 minutes
GC/MS program 16 minutes
Total Cycle Time per sample 30 minutes
 No. SSI-GCMS-1504

Table 2: Compound list and selected ions for the SIM method

Selected Ions for the SIM Mode

Compound Name Abbreviation / Congeners
Quantitation Reference #1 Reference #2
Diisobutyl phthalate DIBP 223.0 205.0 149.0
Dibutyl phthalate DBP 223.0 205.0 149.0
Butyl benzyl phthalate BBP 206.0 91.0 149.0
Di(2-ethylhexyl) phthalate DEHP 279.0 167.0 149.0
Di(n-octyl) phthalate DnOP 279.0 167.0 149.0
Diisononyl phthalate DINP 293.0 167.0 149.0
Diisodecyl phthalate DIDP 307.0 167.0 149.0
Hexabromocyclododecane HBCDD 238.9 560.6
2,2',4,4'-tetrabromodiphenyl ether BDE-47 325.8 483.6
2,2',3,4,4'-pentabromodiphenyl ether BDE-99 403.8 561.6
2,2',4,4',6-pentabromodiphenyl ether BDE-100 403.8 561.6
2,2',4,4',5,5'-hexabromodiphenyl ether BDE-153 483.6 643.5
2,2',4,4',5,6'-hexabromodiphenyl ether BDE-154 483.6 643.5
2,2',3,4,4',5,6'-heptabromodiphenyl ether BDE-183 561.6 721.4
2,2',3,3',4,4',6,6'-Octabromodiphenyl ether +
BDE-197+204 641.5 643.5
2,2',3,4,4',5,6,6'-Octabromodiphenyl ether
Nonabromodiphenyl ethers BDE-206+207+208 719.4 879.2
Decabromodiphenyl ether BDE-209 799.3 959.1
Decabrominated biphenyl BB-209 783.3 785.3

PY-GC/MS Method series of hydrocarbons under the same acquisition

In the micro-furnace of the pyrolyzer, the sample conditions using Automatic Adjust of Retention Time
undergoes a two-step thermal desorption process, (AART) function. A mixture containing saturated
where the temperature increases from 200 °C to 300 hydrocarbon n-isomers from Octane (C8) to
°C at 20 °C per minute, followed by a second Tetracontane (C40) comes with the package and is
temperature ramp from 300 °C to 340 °C at 5 °C used in the AART function. Retention time of all 18
per minute. PBBs, PBDEs and phthalate esters are target compounds is predicted and is used to adjust
released in the temperature controlled micro-furnace the acquisition and data processing retention time
and are transferred to GC/MS for chromatographic parameters in the method.
separation and analysis.
■ Results and Discussion
A simultaneous selected ion monitoring (SIM) and
full scan acquisition method (Scan/SIM) was used on Calibration Standards
the GCMS-QP2010 Ultra. Using a Scan/SIM method Four standards were analyzed using the Scan/SIM
provides enhanced sensitivity of the target method, which include three standards with
compounds by monitoring their signature fragments, phthalates at 0 ppm, 100 ppm and 1000 ppm, and
while simultaneously screening for the unknown one with PBDEs at various concentration between 26
analytes in the full mass range at the same time. ppm and 780 ppm. Total ion chromatograms (TIC)
Because analysis takes place by rapidly alternating for two standards are shown in Figure 2. Figure 3
between the two modes, a fast scan rate is essential shows the SIM chromatographic profiles for the
to assure adequate sensitivity for both SIM and full individual target compounds. DIBP, DBP, BBP, DEHP,
scan modes. and DnOP present as narrow sharp chromatographic
peaks, while the profiles for DINP and DIDP present
The Py-Screener method package includes pre- as a broad cluster of chromatographic peaks due to
registered retention indices for all the target their multiple isomeric components. The area count
compounds. Retention time for the target of mass chromatogram in SIM mode for each
compounds are determined using the retention compound was determined, and applied to the
indices and the retention time for the homologous calibration curve in the quantitation method.
 No. SSI-GCMS-1504

Figure 2: Total ion chromatograms (TIC) for the phthalate and PBDE standards, with full scan mode shown in black and SIM mode
shown in red. Phthalate standard contains seven phthalates at 1000 ppm. The PBDE standard contains PBDEs and PBBs at various
concentrations between 26 and 780 ppm.

Figure 3: Chromatographic profile of the target compounds extracted from SIM chromatogram of the phthalate and PBDE standards.
The primary SIM ions are shown in black, and the secondary reference ions are shown in pink.
 No. SSI-GCMS-1504

LabSolution Insight For this project three polymer samples were analyzed
LabSolution Insight is a software program designed using the PY-GC/MS method described above; they
for simultaneously analyzing data sets from multiple are labeled Blue Conveyor, White Conveyor, and
samples. With LabSolution Insight, quantitative Gasket. A blank sample cup was also analyzed using
results for a complete series of data files can be the same method for quality control purpose. Figure
displayed side-by-side for comparison and QC 4 shows the total ion chromatograms of the three
review. All of the chromatograms from a selected polymer samples. The pre-registered calibration curve
target compound can be displayed simultaneously, from the Py-Screener package was used for
making it easy to review the detected peaks and quantitation. The calibration is based on a one-point
confirm the quantitative results. Color-coded QAQC calibration from analysis of the highest phthalate
flags quickly identify any outliers that require further standard at 1000 ppm, and the PBDE standard. The
examination. Results can be displayed in a variety of quantitation results are categorized into three groups
ways, allowing users to select the view that is best to comply with multiple regulations: below 500 ppm,
suited for their workflow, and when necessary, between 500 and 1500 ppm, and beyond 1500
peaks can be re-integrated and re-quantified directly ppm. All 7 target phthalate compounds from one
from LabSolution Insight. standard and the three samples are displayed side-
by-side in LabSolution Insight, and the outliers with
concentration above 1500 ppm are labeled with
flags, as shown in Figure 5.

Figure 4: Total ion chromatogram from three

samples - Blue Conveyor, White Conveyor, and
Gasket, with full scan mode shown in black and
selected ion monitoring (SIM) mode shown in
blue. Note that the noise level in SIM mode is
reduced significantly compared to full scan
mode.
 No. SSI-GCMS-1504

Figure 5: Quantitative analysis of the seven phthalate analytes in one standard and three polymer samples using the LabSolution Insight
QAQC software. All the phthalate target compounds from three samples with unknown phthalate concentration are displayed with
intensity scaled at the same level as phthalate standard at 1000 ppm. Phthalate content higher than 1500 ppm have been automatically
flagged with a red box by the LabSolution Insight software.
 No. SSI-GCMS-1504

The two samples labeled Blue Conveyor and White Conveyor and White Conveyor samples, which
Conveyor have similar chromatographic profiles, exceed the 0.1% limit in several regulations. The
which both show significant phthalate content Gasket sample shows only low content of DINP and
compared to the Gasket sample. Quantitative DIDP at about 0.03% and 0.02%. All the other types
analysis results on the blank and the three polymer of phthalates and PBDEs are either negligible or non-
samples are shown in table 3. DINP and DIDP were detected in all the three samples.
detected at around 3% and 0.7% in both Blue

Table 3: Quantitative analysis result of three polymer samples

Blue Conveyor White Conveyor
Compound Name Blank (ppm) Gasket (ppm)
(ppm) (ppm)
DIBP ND ND ND 23
DBP 1 ND ND 11
BBP <1 9 ND ND
DEHP <1 12 11 81
DNOP ND ND ND ND
DINP ND 31489 31722 297
DIDP ND 7149 7860 192
HBCDD ND ND ND ND
Tetra-BDE (BDE-47) ND ND ND ND
Penta-BDE (BDE-100) ND ND ND ND
Penta-BDE (BDE-99) ND ND ND ND
Hexa-BDE (BDE-154) ND ND ND ND
Hexa-BDE (BDE-153) ND ND ND ND
Hepta-BDE (BDE-183) ND ND ND ND
Octa-BDE (BDE-197+204) ND ND ND ND
Nona-BDE ND ND ND ND
Deca-BDE (BDE-209) ND ND ND ND

QAQC ■ Summary and Conclusion

Phthalate standards at 0 ppm and 100 ppm were The Py-Screener method package was used to
analyzed using the same method to support quality investigate the phthalates and PBDEs content in
control. In LabSolution Insight, QAQC criteria were three polymer samples. Experimental conditions and
applied so that the data will be highlighted when data processing method are described in detail. The
either of the following two conditions was met: the LabSolution Insight program was used to review
concentration of any of the target compounds in 0 multiple data and flag outliers based on defined
ppm standard exceeds 10 ppm, or the signal to noise QAQC parameters.
ratio of 100 ppm standard falls below 30.
■ References
Since the Py-Screener package was developed for 1. Directive 2002/95/EC, Official Journal of the
phthalate and PBDE screening for several regulations, European Union
the quantitation is only adequate enough to be 2. Public law 110–314, Consumer Product
categorized in those three groups. To achieve further Safety Improvement Act of 2008
accuracy, sohexlet extraction followed by liquid 3. Directive 2005/84/EC, Official Journal of the
injection GC/MS will be required. Regular liquid European Union
injection with capillary column Rxi-1HT (15 m x 0.25 4. Phthalates action plan, U.S. Environmental
mm x 0.1 µm) is recommended instead of pyrolysis. Protection Agency
In this case, the Twin Line MS kit can be used to save 5. Guidance for industry limiting the use of
time on column switching certain phthalates as excipients in CDER-
regulated products, U.S. Department of
Health and Human Services Food and Drug
Administration Center for Drug Evaluation
and Research

First Edition: September 2015

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