:PA-560/6-77-020
ANALYSIS OF
A SERIES OF SAMPLES
FOR
POLYBROMINATED
BIPHENYLS (PBBs)
AUGUST 1977
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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ANALYSIS OF A SERIES OF SAMPLES FOR POLYBROMINATED BIPHENYLS (PBBs)
by
Mitchell D. Erickson, Ruth A. Zweidinger and Edo D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-01-1978
Project Officer
Dr. Vincent J. DeCarlo
Office of Toxic Substances
Washington, D. C. 20460
U. S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D. C. 20460
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DISCLAIMER
This report has been reviewed by the Office of Toxic Substances, U. S.
Environmental Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the views and poli-
cies of the U. S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
ii
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ABSTRACT
Methods for the analysis of polybrominated biphenyls (PBBs) by gas
chromatography/mass spectrometry/computer (GC/MS/COMP) were developed using
a 45 cm x 0.2 cm i.d. glass column packed with 2% OV-101 coated on Gas-
Chrom Q. The column was programmed from 150-300°C at 20°C/min for the
chromatography of mono- through pentabromobiphenyl and from 220-300°C at
12°C/min for hexa- through decabromobiphenyl. Two separate analyses were
required to adequately separate the lower isomers and to yield definitive
peaks for the higher isomers. A total of 80 samples were analyzed by GC/MS
in the Multiple Ion Detection (MID) mode. They contained from undetectable
to 860 pg/ml of PBBs. The higher isomers accounted for the majority of the
PBBs found. Mass spectra obtained during GC/MS analysis of some of the
more highly concentrated samples not only confirmed the presence of PBBs,
but also detected polybrominated biphenyl ethers and other brominated
compounds.
Three commercial samples of decabromobiphenyl ether (C,_Br,00) were
analyzed for impurities by GC/MS using the same conditions as for the
higher PBBs. All three samples contained C12Br-C10 in small amounts and
one sample contained traces of C,2H2BrgO and C-j-HBr-O.
iii
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CONTENTS
Page
Abstract ............................
Figures ............................ vi
Tables ............................. v±ii
Acknowledgements ........................ **
List of Abbreviations ..................... x
1.0 Introduction ..................... 1
2.0 Summary, Conclusions and Recommendations ....... 2
3.0 Objectives ...................... 4
4.0 Method Development .................. 5
4.1 Experimental Apparatus, Instruments and
Chemicals .................... 5
4.2 Direct Probe Mass Spectrometric Analysis of
PBBs ...................... 5
4.3 GC/MS/COMP Analysis of Highly Brominated
PBBs ...................... 7
4.4 GC/MS/COMP Analysis of Lower Brominated
PBBs ...................... 7
4.5 Selection of m/e Ions for MID Analysis ..... 7
4.6 Selection of External Standard ......... 12
4.7 Quantitation .................. 15
4.8 Reproducibility ................. 17
5.0 Sample Receipt .................... 20
6.0 Analysis for PBBs in Environmental Samples ...... 21
6.1 Sample Analysis ................. 21
6.2 Confirmation From Mass Spectral Data ...... 21
7.0 Analysis of Commercial Decabromobiphenyl Ether
Samples for Impurities ................ 31
8.0 References ...................... 33
iv
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Contents (Cont'd)
Page
Appendix A: Description of Mass Spectrometers Used in This
Program 34
Appendix B: TIC Chromatogram and Representative Mass Spectra
of Gas Chromatographic/Mass Spectrometric Analysis of
Sample Number 6077 37
Appendix C: Representative Mass Spectra of Decabromobiphenyl
Ether and Impurities 53
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Figures
Number Page
1 Plot of ion intensities vs. time during direct probe
mass spectrometry analysis of "Soil Extract/Hexane
Spiked sample ..................... 6
2 MID chromatograms of GC/MS analysis of hexa-, octa-,
and decabromobiphenyl standard. Note: nonabromobi-
phenyl impurities (866) ................ 8
3 Total ion current chromatogram of mixed PBB standard
ca. 150 ng of each compound .............. 10
B-l TIC chromatogram of sample number 6077 ........ 38
B-2 Mass spectrum of dibromobenzene (MW=236) and
tetrabromoethylene (MW=344) .............. 39
B-3 Mass spectrum of C^Br^ (MW=329) ........... 40
B-4 Mass spectrum of tetrabromobenzene (MW=394) ...... 41
B-5 Mass spectrum of tribromobiphenyl (MW=391) ...... 42
B-6 Mass spectrum of CJl-Br- (MW=487) ........... 43
B-7 Mass spectrum of hexabromobenzene (MW=552) ...... 44
B-8 Mass spectrum of tetrabromobiphenyl (MW=470) and
C12H6Br40 (MW=486) .................. 45
B-9 Mass spectrum of pentabromobiphenyl (MW=549) and
C12H5Br50 (MW=565) .................. 46
B-10 Mass spectrum of hexabromobiphenyl (MW=628) and
C12H4Br60 (MW=644) .................. 47
B-ll Mass spectrum of heptabromobiphenyl (MW=707) and
C12H3Br?0 (MW=723) .................. 48
B-12 Mass spectrum of octabromobiphenyl (MW=786) and
C12H2Br8° tt1^802) .................. 49
B-13 Mass spectrum of nonabromobiphenyl (MW=866) and
C12HBrgO (MW=881) ................... 50
vi
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Figures (Cont'd)
Page
Mass spectrum of decabromobiphenyl (MW=944) 51
Mass spectrum of C12Br100 (MW=960) 52
Representative mass spectrum of decabromobiphenyl
ether C12Br1Q0 (m/e = 960) and C12Br9C10 (m/e = 914)
which coeluted 54
C-2 Mass spectrum of CLJJrgHO (m/e = 880) found in
DECABROM-DW sample 55
C-3 Mass spectrum of cioBr8H2° ^e = 802^ found in
DECABROM-DW sample. Note: Trace amount of sample
approaching the digitization level 56
vii
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Tables
Number
1 Retention Times for PBB Standards Using GC Conditions for
Higher Isomers 9
2 Retention Times for Standards Using GC Conditions for
Lower Isomers H
3 Intensities of Isotopic Peaks Relative to the Molecular
Ion for Polybrominated Compounds 13
4 MID Ions Selected for PBB Analysis 14
5 Relative Molar Response Values Determined for PBBs ... 16
6 Triplicate Analysis of Sample Number 6077 Illustrating
Reproducibility for Lower Isomers 18
7 Replicate Analysis of Sample Number 6058 Illustrating
Reproducibility for Higher Isomers 19
8 Estimated Levels of PBBs in Blank and Spiked
Extracts 22
9 Estimated Levels of PBBs in Environmental
Samples 24
10 Brominated Compounds Detected in Sample Number 6077 By
GC/MS Analysis 28
11 Brominated Compounds in Sample Number 6058 30
viii
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ACKNOWLEDGEMENTS
The authors wish to thank Drs. J. T. Bursey, D. Rosenthai and M. E.
Wall and Mr. L. Kelner of the Research Triangle Institute (RTI) for their
assistance and encouragement and Drs. V. J. DeCarlo and G. E. Parris,
Environmental Protection Agency, Office of Toxic Substances, Washington,
D. C. for their valuable discussions. We also wish to thank Messrs. C. L.
Stratton and S. A. Whitlock of Environmental Sciences and Engineering
(ES&E), Incorporated, Gainesville, Florida whose earnest participation in
the sample collection and preparation was vital to the successful completion
of this cooperative effort.
ix
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LIST OF ABBREVIATIONS
ES&E - Environmental Sciences and Engineering, Inc., Gainesville,
Florida
GC Gas Chromatography
GC/MS - Gas Chromatography/Mass Spectrometry/Computer
M - Parent Ion in Mass Spectrum
m/e - Mass-to-charge ratio
MID - Multiple Ion Detection
OCN - Octachloronaphthalene
PBB - Polybrominated biphenyls
RMR - Relative Molar Response
RSD - Relative Standard Deviation
SD - Standard Deviation
TIC - Total Ion Current
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1.0 INTRODUCTION
Polybrominated biphenyls (PBBs) are used extensively as flame
retardants for polymers, textiles, and other materials. The major
component of the most common commercial mixture, Fire Master PB-6 , is
(3-7)
hexabromobiphenyl . Concern about the environmental impact and health
effects of wide spread use of PBBs has been aroused by a recent major
environmental catastrophe in Michigan. Their chemical similarity to
polychlorinated biphenyls (PCS) and polychlorinated naphthalenes (PCN) has
raised the question of bioconcentration and toxicity to the point to warrant
a test of the carcinogenicity of hexabromobiphenyl by the National Cancer
(9)
Institute Bioassay Program.
Spurred by the Michigan disaster, analytical methodologies have been
developed and applied to feeds , dairy products and soils. '
Although extensive analytical work is being carried out with respect to
samples originating in Michigan, little attention has been directed at more
generalized pollution resulting from normal manufacture and use of PBBs
throughout the United States. This research was designed to study potential
industrial sources of PBBs and to assess their environmental occurrence.
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2.0 SUMMARY, CONCLUSIONS AND RECOMMENDATIONS
Methods for the analysis of polybrominated biphenyls (PBBs) by gas
chromatography/mass spectrometry/computer (GC/MS/COMP) were developed.
Mono- through pentabromobiphenyls were analyzed using a 45 cm x 0.2 cm i.d.
glass column packed with 2% OV-101 coated on Gas-Chrom Q and a flow rate of
30 cc/min helium. The column temperature was 150° initially, raised at
25°/min to 300°, then held constant. Hexa- through decabromobiphenyls were
analyzed using the same gas chromatographic (GC) conditions as for the
lower isomers except the flow rate was 20 cc/min and the column temperature
was 220° initially, programmed at 12°/min to 300°, then held constant.
Samples were analyzed using the mass spectrometer in the Multiple Ion
Detection (MID) mode to achieve greater sensitivity.
A total of 87 samples were received from Environmental Sciences and
Engineering (ES&E), Gainesville, Florida who collected, extracted, and
added an external standard to the samples (EPA Contract No. 69-01-3248).
The samples received included not only extracts of environmental samples,
but also blanks, spikes, duplicates, etc. for quality control purposes.
The samples were analyzed for PBBs (both high and low levels of
bromination) . The total amounts of PBBs found ranged from undetectable to
860 (Jg/ml. The higher isomers accounted for the majority of the PBBs
found.
Mass spectra obtained during GC/MS analysis of some of the more highly
concentrated samples confirmed the presence of PBBs and polybrominated
biphenyl ethers and other brominated aromatics were also identified.
Three commercial samples of decabromobiphenyl ether (ci2Brio°^ were
analyzed by GC/MS to determine if impurities were present. The gas chromato-
graphic conditions were the same as those used for the higher PBBs. All
three samples were found to contain C,2Br_C10 in small amounts and one
sample contained traces of C.-HBrO and CJffirO. Further research in
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this area should be directed at the unusual fragmentation of decabromo-
biphenyl ether observed in the mass spectra. The trace impurities present
in decabromobiphenyl ether could best be further investigated by high
performance liquid chromatographic fractionation of large amounts of the
sample to concentrate these impurities for mass spectrometric identification.
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3.0 OBJECTIVES
The major emphasis of this research was to analyze a series of environ-
mental samples for PBBs by GC/MS. The specific objectives were to (1)
develop gas chromatographic conditions which separated the PBB components
and elutes the compounds of interest within a short time with definitive,
easily quantifiable peaks; (2) develop a quantification procedure for the
PBBs found in the samples; (3) analyze the samples; (4) interpret the data;
(5) confirm the presence of PBBs in some of the more highly concentrated
samples; and (6) analyze three samples of commercially available decabromo-
biphenyl ether to determine gas chromatographable impurities.
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4.0 METHOD DEVELOPMENT
Methods were developed for the analysis of PBBs by GC/MS using a short
GC column. Each sample was analyzed twice, once separating the lower
isomers and once eluting the higher isomers quickly to provide sharp peaks
for detection and quantitation. Preliminary investigation using direct
probe mass spectrometry for analysis of samples was shown not to be feasible.
The development of analytical conditions is discussed in detail below.
4.1 EXPERIMENTAL APPARATUS, INSTRUMENTS AND CHEMICALS
Toluene (Burdick and Jackson, Muskegon, Michigan) was redistilled
prior to use. Polybrominated biphenyls (4-bromobiphenyl, 4,4'-dibromo-
biphenyl, 2,2',5-tribromobiphenyl, 2,2',5,5'-tetrabromobiphenyl, 2,2',4,5,6-
pentabromobiphenyl, 2,2',4,4',5,5'-hexabromobiphenyl, 2,2',3,3',5,5',6,6'-
octabromobiphenyl, and decabromobiphenyl) and octachloronaphthalene were
purchased from RFR Corporation, Hope, Rhode Island.
Analysis of all samples was accomplished using a Finnigan 3300 quadru-
pole GC/MS equipped with a PDP/12 computer. Direct probe analysis of a
decabromobiphenyl ether sample was accomplished using an AEI MS 902 high
resolution mass spectrometer. Complete descriptions of the instruments are
presented in Appendix A.
4.2 DIRECT PROBE MASS SPECTROMETRIC ANALYSIS OF PBBs
Initial experiments using direct probe mass spectrometry indicated
that this technique potentially could be an easy, sensitive, and very quick
method of analyzing samples for the higher order PBB isomers. This avenue
was pursued because these isomers were found to chromatograph poorly when
using instrumental conditions for the analysis of PCBs and PCNs. Although
the sensitivity of the direct probe for standards was excellent (<0.5 ng)
and the sample analysis was completed within about 2-3 minutes (Figure 1),
the procedure was non-reproducible. Furthermore, it suffered from non-
specificity for environmental samples.
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180.0
80.0J
01
01
60.0-
e
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4.3 GC/MS/COMP ANALYSIS OF HIGHLY BROMINATED PBBs
Initial experiments indicated that, under the conditions necessary for
resolution of the lower brominated PBBs, the highly brominated PBBs had
long retention times and eluted as broad, diffuse peaks. Since such broad
peaks were not conducive to quantification and reduced the sensitivity of
the analysis, GC conditions were sought which eluted these compounds quickly
as definitive peaks. These conditions, which were adopted for the analysis
of samples, required a 45 cm x 0.2 cm i.d. glass column packed with 2%
OV-101 coated on Gas-Chrom Q and a flow rate of 20 cc/min helium. The
temperature of the molecular separator was 280°, the injection port 270°,
and the GC column 220° initially, and then programmed at 12°/min to 300°.
Under these conditions, hexa-, hepta-, octa-, nona-, and decabromobiphenyls
and the octachloronaphthalene standard were resolved as definitive peaks.
Decabromobiphenyl eluted within 6 min (Figure 2, Table 1). Hepta- and
nonabromobiphenyl were not commercially available, but were found to be
impurities in the standards. As seen in Figure 2, both isomers of nona-
bromobiphenyl are present, with retention times of 4.6 and 5.2 min.
The mass spectrometer ionization volatage was 70 eV (nominal) and the
electron multiplier voltage was between 1.8-2.2 kV. The spectrometer was
either scanned from m/e 100-1000 or used in the MID mode as discussed
below.
4.4 GC/MS/COMP ANALYSIS OF LOWER BROMINATED PBBs
Gas chromatographic conditions were developed for separating the lower
(mono- through penta-) brominated PBBs which also eluted the higher isomers
within a reasonable time in preparation for another injection. The GC/MS
conditions were the same as described above, except the column temperature
was 150° initially, raised at 20°/min to 300°, then held constant, and the
flow rate was 30 cc/min. Figure 3 and Table 2 illustrate the separations
and retention times obtained under these conditions.
4.5 SELECTION OF m/e IONS FOR MID ANALYSIS
Multiple ion detection (MID) is an operational mode for gas chromato-
graph/mass spectrometers where several m/e values are monitored through the
chromatogram. To obtain each m/e value preset voltages are step-jumped at
short time intervals. Since this technique also allows integration of ion
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(75
z
UJ
I-
LU
942 * 10
TIME (min)
Figure 2. HID chromatograms from GC/MS analysis
of hexa-, octa-, and decabromobiphenyl
standard. Note: nonabromobiphenyl
impurities (m/e 866).
8
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Table 1. RETENTION TIMES FOR PBB STANDARDS USING GC
CONDITIONS FOR HIGHER ISOMERS*
Compound Retention Time (min)
octachloronaphthalene (standard) 1.3
2,2',4,4',5,5'-hexabromobiphenyl 1.7
Q
heptabromobiphenyl 3.1
2,2',3,3',5,5',6,6'-octabromobiphenyl 3.8
^
nonab romobipheny1 4.4
decab romob ipheny1 5.8
aSee Figure 2 for MID chromatogram. See text for conditions.
In cases where more than one isomer was present due to impure standards,
the retention time was listed for most intense peak.
CImpurities in standards; positional isomers not identified.
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H
a
llHJ.ll-
UU.H
60.0-
40. n
ro.fi-
.0-
TTTfTToi ii'iimr* 'TiTr
*irr-»
5
iTrTr|rTi-ntTrt|ri«*Ttr» lytm. «ri| t
Time (min)
ON
rir«
Figure 3. Total ion current chromatogram of mixed PBB standard ca. 150 ng of each
compound.
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Table 2. RETENTION TIMES FOR STANDARDS USING GC
CONDITIONS FOR LOWER ISOMERS3
Compound Retention Time (min)
4-bromobiphenyl 2.7
4,4'-dibromobiphenyl 5.6
2,2',5-tribromobipheny1 5.9
2,2*,5,5'-tetrabromobiphenyl 8.0
2,2',4,5,6-pentabromobipheny1 8.8
octachloronaphthalene 9.9
2,2',4,4',5,5'-hexabromobipheny1 10.3
b
heptabromobiphenyl 11.7
2,2',3,3',5,5',6,6'-octabromobiphenyl 13.2
nonab romob ipheny 1b 14.1
decabromobiphenyl 14.7
aSee Figure 3 for TIC chromatogram. Conditions for lower isomers, see
text.
Impurities in standards; positional isomers not identified.
11
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intensity for a longer time period for the desired ions than in the customary
full-scan mode, the sensitivity of the instrument generally is increased by
approximately two orders of magnitude. By judicious selection of m/e
values for monitoring specific compounds, interference by unwanted compounds
can usually be minimized.
Eight m/e ions were selected for monitoring the PBBs with the ninth
channel devoted to detection of the octachloronaphthalene external standard
(Table 4). Ions were chosen from the parent cluster even though they
were not necessarily the most intense to reduce the probability of inter-
ference from fragments of other PBBs or compounds.
The m/e ions selected were generally those most intense in the parent
cluster. The natural abundance of two major bromine isotopes (atomic
weights of 79 and 81) yields a cluster of ions with the different isotopic
permutations as shown in Table 3. This table illustrates clearly that the
parent ion (M) was not nearly as intense as ions at or near the centroid of
the cluster.
The m/e ions selected for MID analysis are shown in Table 4. Two m/e
ions are listed for each isomer and to the extent possible, both ions were
used to confirm the presence of brominated compounds. The relative intensity
of the two m/e ions as calculated from the theoretical isotopic abundance
was used for comparing and confirming the identity and purity of the PBBs
monitored in environmental samples.
4.6 SELECTION OF EXTERNAL STANDARD
Octachloronaphthalene (OCN) was selected as an external standard based
on its similar retention time to the middle isomers of the PBBs, its high
molecular weight, unique parent ion, and low likelihood of occurrence in
these environmental samples. The environmental occurrence of OCN has been
shown to be relatively infrequent even in areas where high concentrations
of other polychlorinated naphthalenes were observed. The high molecular
weight and unique parent ion of OCN reduced the chance of interference from
background or sample components. In addition, the low volatility of OCN
decreased the possibility of loss prior to analysis.
12
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Table 3. INTENSITIES OF ISOTOPIC PEAKS RELATIVE TO THE MOLECULAR ION FOR
POLYBROMINATED COMPOUNDS
Degree of
Bromiuation
Br
Br2
Br3
Br4
Br5
Br6
Br7
Br8
Br9
Brio
M
100
100
100
100
100
100
100
100
100
100
M + 2
97.8
195
293
391
489
587
685
783
881
979
M + 4
95
286
575
958
1436
2011
2682
3440
4310
M + 6
93
375
937
1875
3280
5249
7873
11247
M + 8
92
459
1376
3210
6421
11557
19262
M + 10
90
539
1885
5027
11310
22620
M + 12 M + 14
88
615 86
2460 687
7379 3095
18447 10315
M + 16 M + 18 M + 20
84
757 82
3786 823 81
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Table 4. MID IONS SELECTED FOR PBB ANALYSIS
PCB Isomers
C H B
12 9 r
C12H8Br2
C12H7Br3
C12H6Br4
C12H5Br5
C12H4Br6
C12H3Br7
C12H2Br8
C12HBr9
C12Br10
M*
232
310
388
466
544
622
700
778
856
934
MID Ionsb
232,
312,
390,
470,
548,
628,
706,
788,
866,
942,
234
310
392
472
550
630
708
784
862
946
M = nominal molecular weight based on Br = 79
Ions listed in order of "primary" and "secondary"
14
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4.7 QUANTITATION
Quantisation was achieved by comparing the computer-calculated inte-
grated area of the PBB isomers with the integrated response for a known
amount of octachloronaphthalene. To compensate for differences in ioniza-
tion cross-section, the relative molar response of available PBB standards
was obtained.
The calculation of the relative molar response (RMR) factor allows the
estimation of the levels of sample components without establishing a
calibration curve. The RMR is calculated as the integrated peak area of a
known amount of the compound, AV. , with respect to the integrated peak
area of a known amount of standard, A° . (in this case octachloronaphtha-
S uQ
lene) , according to the equation
RMR = Aunk/molesunk = (Aunk} (mwunk) (gstd} (Equation 1)
A° /moles fc. (A° )(mw t,)(g .)
std std std std 6unk
From this calculated value, the concentration of an identified compound in
a sample is calculated by rearranging Equation 1 to give
g . = (Aunk) (""Wk^ (gstd^ (Equation 2)
CAstd)(niWstd)(RMR)
The use of RMR for quantitation by GC/MS has been successful in re-
peated applications to similar research problems .
The RMRs for the available PBB isomers were calculated from the numeri-
cal integrations of peaks observed in the appropriate MID channel. The
RMRs listed in Table 5 are mean values of three injections of each of three
replicate standard mixtures. The standard of 2,2' ,3,3' ,5,5" ,6,6'- octabromo-
biphenyl was found to be severely contaminated by hepta- and nonabromobi-
phenyl isomers, so they were not used in the RMR calculations. The RMR
values listed for hepta-, octa-, and nonabromobiphenyl were calculated from
a linear interpolation between the RMR values obtained for hexa- and deca-
bromobiphenyl.
Several qualifications must be recognized regarding the RMR values
presented in Table 5. The values obtained for these positional isomers
were probably not highly precise for other isomers since differences in the
15
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Table 5. RELATIVE MOLAR RESPONSE VALUES DETERMINED FOR PBBs
Compound
4-b r omob ipheny 1
4,4' -dibromobiphenyl
2,2', 5-tribromobiphenyl
2 , 2 ' , 5 , 5 ' - tetrabromob ipheny 1
2 , 2 ' , 4 , 5 , 6-pentabromobiphenyl
2, 2', 4, 4', 5, 5' -hexabr omob ipheny 1
hep tabr omob ipheny 1
octabromobiphenyl
nonab r omob ipheny 1
decabromobiphenyl
RMRa
1.34
2.09
1.04
1.11
1.14
1.00
0.77
0.53
0.29
0.065
SDb
0.64
0.67
0.35
0.30
0.30
0.33
0.023
RSDC
0.48
0.32
0.33
0.27
0.27
0.33
0.35
Mean Relative Molar Response. Nine determinations: three injections
each of three replicate standards.
b.
Standard Deviation
c
Relative Standard Deviation = SD/RMR
value obtained by linear interpolation between values for 2,2',4,4*,5,5'-
hexabromobiphenyl and decabromobiphenyl
16
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ionization cross-section may occur. The purity of the standards in some
cases were questionable; a small quantity of nona- and hepta- were found in
the decabromobiphenyl and hexabromobiphenyl samples, respectively. Both
impurities were judged to be <5% and were ignored for the RMR determinations.
The relative molar response depends not only on the ionization cross-section,
but also on instrumental parameters, including the ion slit widths, exact
mass setting, and electronic drift. These considerations were more pro-
nounced over the wider mass ranges used in P6B analysis. Thus, the accuracy
of PBB analysis is highly dependent upon the precise determinations of the
RMR factor.
4.8 REPRODUCIBILITY
Two samples were analyzed by multiple injections to check the reproduci-
bility of analysis for the various isomers and over the range of PBB levels
found. Table 6 summarizes the results for the triplicate analysis of
sample number 6077 for the lower isomers. The reproducibility is better
than +10%. Table 7 illustrates the replicate analyses of sample 6058 for
the higher isomers. The lack of reproducibility observed for hexa- and
heptabromobiphenyl was attributed to the low concentrations, which approached
the detection limit. The reproducibility of the analyses for the higher
PBB isomers was somewhat impaired by instrumental instabilities at higher
m/e values. It is important to note the agreement between the first analysis
and the subsequent analyses which were obtained at different time periods
(days). This agreement supports the use of RMR values for quantitation.
17
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Table 6. TRIPLICATE ANALYSIS OF SAMPLE NUMBER 6077 ILLUSTRATING
REPRODUCIBILITY FOR LOWER ISOMERS
Analysis
First
Second
Third
Mean
SD
RSD
Concentration Found (ug/ml)
C12H9Br C12H8Br2
a 4.92
a 4.29
a 3.95
4.39
0.41
0.093
C12H7Br3
8.56
8.65
7.84
8.34
0.44
0.053
C12H6Br4 C12H5Br5
1.15
1.05
1.00
1.05
0.097
0.093
Severe hydrocarbon interference prevented its accurate determination.
Estimated at about 2 Jig/ml.
18
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Table 7. REPLICATE ANALYSIS OF SAMPLE NUMBER 6058 ILLUSTRATING
REPRODUCIBILITY FOR HIGHER ISOMERS
Analysis
First
Second
Third
Fourth
Fifth
Mean
SD
RSD
C12H4Bl
0.046
0.012
0.023
0.042
0.030
0.017
0.52
Concentration
:6 C12H3Br7
0.21
0.35
0.40
0.17
0.29
0.11
0.39
Found (yg/ml)
C12H2H8 (
0.76
0.73
0.97
0.85
1.05
0.87
0.14
0.16
-it**.
2.36
2.08
3.44
3.86
3.53
3.06
0.78
0.26
C12Br10
85.1
66.6
104
124
110
97.7
22.3
0.23
aSecond through Fifth analyses performed consecutively. First analysis
performed one month earlier.
19
-------
5.0 SAMPLE RECEIPT
Samples were received from ES&E generally in 1.0 ml conical reaction
A
vials with Teflon -lined septum caps. Each sample had been spiked with 5
ng/pl octachloronaphthalene as an external standard for retention time
correlation and quantification. Samples were shipped in ice and were
stored at 5° following receipt. Each sample was logged for quality control
purposes (a sample log book was used to record the status of each sample)
as it was processed and the receipt and numerical coding confirmed via
telephone with personnel at ES&E.
A total of 87 samples were received, as listed in Tables 8 and 9 in
Section 6.
20
-------
6.0 ANALYSIS OF ENVIRONMENTAL SAMPLES FOR PBBs
6.1 SAMPLE ANALYSIS
Using the GC/MS methods discussed in Section 4, the samples were
analyzed first for the higher PBB isomers (hexa- through decabromobiphenyl)
and then for the lower isomers (mono- through pentabromobiphenyl). On the
advice of the Project Officer, some of the samples for which no higher
isomers were detected were not analyzed for the lower isomers. In addition,
the last batch of samples was received after the period of performance
ended and were not analyzed.
The results of the analysis of blanks and spiked samples are presented
in Table 8. Table 9 summarizes the results of the analysis of numbered
samples and numbered spikes.
A sample of the OCN solution (5 ng/yl) used to spike the samples were
obtained for ES&E and compared with the OCN solution (4.9 ng/yl) prepared
in house. Replicate analyses of the two samples yielded integrated areas
of 485.4 +25.5 and 313.5 + 18.2, respectively. Taking into account the
calculated concentrations, the OCN sample from ES&E was 1.52 times more
concentrated that that prepared in house. Since the value directly affects
the concentrations in the sample (see Equation 2), the values in Tables
8 and 9 reflect this correction.
6.2 CONFIRMATION FROM MASS SPECTRAL DATA
Several samples contained sufficient concentrations of PBBs for acquisi-
tion of full mass spectra. These analyses confirmed the presence of PBB
isomers and several other related compounds were also detected.
Sample number 6077 contained a large number of bromobenzene, bromo-
toluene, and bromobiphenyl ether species as shown in Table 10. The total
ion current (TIC) chromatogram and representative mass spectra are presented
in Appendix B.
21
-------
Table 8. ESTIMATED LEVELS OF PBBs IN BLANK AND SPIKED EXTRACTS
ts>
10
Sample8
Blank Toluene (Nan)
Toluene Filter Wash
Toluene Filter Wash
Toluene Filter Wash
Toluene Filter Wash
PUF Extract Spiked
PUF Extract Blank
H20 Extract Spiked
H_0 Extract Blank
Soil Extract Spiked
Soil Extract Blank
Spiking Solution
Blank Sediment Extract
Spiked Sediment Extract
Spiking Solution
Blank-PB-4
Blank-Hex-1
Blank-Hex-2
Blank-llex-3
Blank Tissue
Blank
C12..9Btb
c
__
27
12
0.05
25e
__
21f
c
13f
NA8
NA
NA
NA
NA
NA
W,
>85d
51
0.2
80e
53f
f
41*
NA
NA
NA
NA
NA
NA
W<3
__
54
0.08
27
0.4
44e
26f
f
15*
NA
NA
NA
NA
NA
NA
C12»6Br4
__
~
0.09
0.09
~
0.6
5.9
NA
NA
NA
NA
NA
NA
Amount
--
0.06
0.06
0.09
0.5
3.5
NA
NA
NA
NA
NA
NA
Found (Ug/ml)
C12H4Br6 C12H3Br7 C12H2Br8 C12HBr9 C12BrlC
__
______
__ __ __
0.04 .08 .3 2.1 7.9
0.09
0.08
0.06 0.06 2.1 a.8
0.6 --
f
C -I* __ __
J 0 J -"" »" "» ^^
9.1 7.4 1.8 1.2 14
_________
__
__
( Total
__.
>180
0.3
90
0.8
170
100
84
33
~
-------
Table 8. (Cont'd)
aSample code as received from ES&E. For amounts added see ES&E
report for Contract No. 69-01-3248.
In cases where positional isomers were observed, the value presented
is a total integration of these isomers.
Undetected
Detector saturated
e
Average of three determinations
Average of two determinations
%A = not analyzed after consultation with the project officer
23
-------
Table 9. ESTIMATED LEVELS OF PBBs IN ENVIRONMENTAL SAMPLES
Amount Found (tig/ml)
Sample*
6S09-SO
6701-SO
6703-SO
6705-50
6709-SO
6717-50
6718-50
6791-SO
6794-50
6797-50
6004-SED
6006-W
6020-SED
604 7-W
6054 -W
6058-W
6064-W
6069-W
6077-SED
6079-W
6406-SED
C12l,9Br" C12l.aBr2 C12,,7Br3 C^^Br, C^Ir, C^ir.
0.5 -C ~ - - Td
__ __ ___ _ __ ff
T
T
1.6
0.2
" . ~ 0.2
T
0.2
0.9
0.5
NAC NA NA NA NA
0.1
NA NA NA NA NA
NA NA NA NA NA
Tf
1.4
NA NA NA NA NA
28 4.4h 8.4h l.lh 7.9
-- 0.2 0.6
NA NA NA NA NA
C12H3Br7
T
~
0.1
0.7
1.1
0.1
.1
0.3f
0.5
~
6.8
0.5
C12»2Br8
0.6
1.2
~
1.8
~
0.9f
0.3
7.4
0.5
C12HBr9
~
~
2.5
0.4
4.9
~
3.0f
0.3
~
4.7
3.0
C12Br10
T
13
4.0
~
29
29
98f
25
820
14
Total
0.6
T
T
T
1.6
14
8.7
T
29
38
0.6
0.2
~
100f
28
860
19
-------
Table 9. (Cont'd)
Sample*
6406-Splke SED
6512-W
6512-41 Spike
6515-W
6522-SED
6523-SED
6524-W
6703-Splke
6710-A
6711-A
6725-A
6726-A
6737-A
6738-A
6766-A
6767-A
6010-TS
6015-TS
6016-TS
6017-TS
Amount
C12H9Btb C12H8Br2 C^B^ C^Br^ C12H5Br5
NA NA NA NA NA
NA NA NA NA NA
~ _ _
_
NA NA NA NA NA
_
__
NA NA NA NA NA
NA NA NA NA NA
~w «_ _
__ -_
Found (lig/ml)
C12H4Br6 C12H3Bt7
4.7 0.3
__
T
0.1 0.1
__
0.6 0.3
0.1 0.1
4.9 0.5
0.1
0.1
T
*P «*
0.1
__
__
__ «
0.51 0.61
m _
0.3
C12H2Br8 C12HBr9 C12Br10 Total
0.1 0.9 2.7 8.8
T
0.8 0.9 2.6 4.6
-- 0.9
0.3 0.3 0.8 1.7
0.3 0.3 2.7 8.9
0.1
0.1
_ T
«. » T
o.i
__
_ _
__ _ _ __ '
0.8l 2.41 13. 21 181
_« T
0.3
-------
Table 9. (Cont'd)
Sample
6018-TS
6021-TS
6048-TS
6060-TS
6060-TS-Spike
6080-TS
6081-TS
6082-TS
6083-TS
6084-TS
6085-TS
6085-TS-Spike
6086-TS
6518-TS
652S-TS
6526-TS
6527-TS
6528-TS
6519-TS
Cl2H9Br
NA
NA
NA
NA
NA
NA
NA
__
C12U8Br2 C12H7Br3
NA NA
« __
NA NA
NA NNA
3
NA NA
NA NA
NA NA
NA NA
__ __
Amount
C12H6Br4 C12H5Br5
NA NA
. __
NA NA
NA NA
_
NA NA
__
_
NA NA
NA NA
NA NA
__
__ __
Found (ug/ml)
C12H4Br6 C12H3Br7 C12H2Br8 C12HBr9
__
0.1 0.1 0.1 0.9
0.8 25
3.51
3.81 0.51 0.31 3.51
__ *|*
-_
0.1 4.9
7.4 0.6 0.3 0.9
.06
0.5
~
0.3
0.1
T -- 0.5
C12Br10
1.5
470
411
471
T
~
--
62
7.6
__
1.1
Total
~
2.9
490
45l
551
T
3
67
17
.06
0.5
~
0.3
1.3
0.5
-------
Table 9. (Cont'd)
Amount Found (pg/ml)
Sample
Blank-Clay^
6020-ClayJ
60461
6046-ClayJ
6521^
6521-ClayJ
C12H9Br
NA
NA
NA
NA
NA
NA
C12H8Br2
NA
NA
NA
NA
NA
NA
C12l.7Br3
NA
NA
NA
NA
NA
NA
C12H6Br4
NA
NA
NA
NA
NA
NA
C12H5Br5
NA
NA
NA
NA
NA
NA
C12H4Brfi
NA
NA
NA
NA
NA
NA
C12H3Br7
NA
NA
NA
NA
NA
NA
C12H2Br8
NA
NA
NA
NA
NA
NA
C^HBr,
NA
NA
NA
NA
NA
NA
C12Br10
NA
NA
NA
NA
NA
NA
Total
__
_
~
Sample Code as received from ES&E - SO - soil, W - water, A - air, TS - tissue, SED - sediment
In cases where positional isomers were observed, the value presented is a total integration of these isomers
°Undetectable
Trace (generally <0.1 pg/ml)
eNA - not analyzed after consultation with project officer
Mean of five determinations. See Table 7
Value approximate due to severe hydrocarbon interference
Average of three determinations. See Table 6
Interferent with OCN peak. Values are minima
j
Samples not analyzed. Received from ES4E after end of performance period
-------
Table 10. BROMINATED COMPOUNDS DETECTED IN SAMPLE NUMBER 6077 BY
GC/MS ANALYSIS
Compound3 Retention Time
(min)
Wr2 °'1
C2Br4 0.1
C?H5Br3 2.6
C6H2Br4 3.7
C12H7Br3 8.5
C?H3Br5 9.5
C6Br6 10'9
C12H6Br4 11.2
CTJ *D^> C\ 119
19 A A *
C12H5Br5 12.1 (0.9-1.8)
^ TJ Tl^ O 19 1 ^1 7^
C10H.Br, 12.5-12.7 (2.2)
I/ 4 O
C12H4Br60 12.5-12.7 (2.5)
C12H3Br7 13.3-13.7 (2.8-3.3)
C12H2Br8 13.8-14.3 (4.0)
13.3-13.7 (3.3)
13.8-14.3 (4.0)
14.1-15.4 (4.7)
C12HBr9 14.3-15.4 (4.7)
C HBr00 15.4
C12Br10 (6.0)
C12Br100 (7.5)
xhe bromobiphenyls were confirmed by comparison of mass spectra and
retention times with authentic standards.
GC conditions: 2% OV-101 coated on Gas-Chrom Q; column: 45 cm x 0.2 cm
i.d., 20 cc/min helium, 100° initial, programmed at 12°/min to 300°.
temperature conditions were 220° initial, programmed at 12°/min to 300°,
for these values in parentheses.
28
-------
Analysis by GC/MS of sample number 6058 indicated the presence of
the PBBs and polybrominated biphenyl ethers listed in Table 11.
Decabromobiphenyl was confirmed by the mass spectra obtained from
GC/MS analysis of sample number 6048.
29
-------
Table 11. BROMINATED COMPOUNDS IN SAMPLE NUMBER 6058
,a Retention Time
Compound (m±n)
C12H4Br60 2.3
C12H3Br70 3.7
4.6-4.9
4.7-4.9
C12BrM 6.2
C12Br1Q0 7.4
xhe bromobiphenyls were confirmed by comparison of mass spectra and
retention times with authentic standards.
GC conditions: 2% OV-101 coated on Gas Chrom Q; column: 45 cm x 0.2 i.d.,
20 cc/min helium, 220° initial, programmed at 12°/min to 300°.
30
-------
7.0 ANALYSIS OF COMMERCIAL DECABROMOBIPHENYL ETHER SAMPLES FOR
IMPURITIES
Three commercial samples of decabromobiphenyl ether ("Decabrom",
C12Br10°^ were analyzed b7 GC/MS and direct probe mass spectrometry for
characterization of any potentially toxic impurities.
One sample of decabromobiphenyl ether (DECABROM-PS) was purchased from
Polyscience, Inc., Warrington, Pennsylvania, Lot No. 5-46-8.
Another sample was obtained through the courtesy of Great Lakes
Chemical Co., West Lafayette, Indiana, "Decabromobiphenyl Oxide, Great
Lakes DE-83, Ref. No. NY-8860, 6-2-77". This sample is hereafter referred
to as DECABROM-GRL.
The third sample was obtained through the courtesy of Dow Chemical
Co., Midland, Michigan, Decabromobiphenyl Oxide, FR 300 BA, Lot No. 06076-
2, 2# sample. This sample is hereafter referred to as DECABROM-DW.
Solutions of each sample were prepared at 1 mg/ml in toluene. The
samples were subjected to GC/MS/COMP analysis on a Finnigan 3300 system
using the chromatographic conditions for the higher PBBs (45 cm x 0.2 cm
i.d. glass column packed with 2% OV-101 on Gas-Chrom Q; 220° initial, pro-
grammed at 12°/min to 300°; 30 cc/min helium carrier gas).
The samples were found to contain primarily Ci2Br10° witn sma11 amounts
of C,2BrgC10. DDECABROM-DW also contained traces of C12H2BrgO and C12HBrgO.
These results are summarized in Figures C-l through C-3. Two ion clusters
were present in the mass spectrum of C,JBr.00 and C12BrgC10 (Figure C-l)
which were not readily assignable as fragments of either molecule. These
clusters, centered at m/e 692 and m/e 613, do not result from simple debromi-
nation or dechlorination of either of the two molecules, so the samples
were examined further to determine if additional impurities were present.
Close examination of the GC/MS data indicated that these clusters co-eluted
31
-------
with the other ions attributed to C,9Br,00 and its fragments. Exact mass
measurements (to 4 decimal places) were made by direct probe mass spectral
analysis using an AEI MS 902 (see Appenix A for a description of the system)
Computerized peak matching found excellent correlation of C,,Br7 with the
ion cluster centered at m/e 692 and a mixture of C..,Br, and C,,Br,.H with
the ion cluster centered at m/e 613. Both the GC/MS and direct probe MS
data indicated that C,,Br_ and C,,Br, are fragments of C,0BrlnO, implying
11 / 11 O Lt- 1U
an unusual loss of CO from the diphenyl ether molecule. The origin of the
C,,Br,H species remain unidentified.
In summary, the impurities found in three decabromobiphenyl ether
samples were C,2BrgC10 (three samples), C,2H2BrgO (one sample), and C
(one sample).
32
-------
8.0 REFERENCES
1. G. Sundstrom, 0. Hutzinger, S. Safe and V. Zitko, The Science of the
Total Environment, 6, 15 (1976).
2. Michigan Chemical Corporation, St. Louis, Michigan.
3. W. H. Gutenmann and D. J. Lisk, J. Agr. Food Chem., 23, 1005 (1976).
4. N. V. Fehringer, J. Ass. Offic. Anal. Chem., 58, 978 (1975).
5. N. V. Fehringer, J. Ass. Offic. Anal. Chem., 58, 1206 (1975).
6. L. W. Jacobs, S.-F. Chou and J. J. Tiedje, J. Agr. Food Chem., 24,
1198 (1976).
7. A. B. Filanow, L. W. Jacobs, and M. M. Mortland, J. Agr. Food Chem.,
24, 1201 (1976).
8. L. 0. Ruzo, G. Sundstrom, 0. Hutzinger and S. Safe, J. Agr. Food
Chem., 24, 1082 (1976).
9. Pest. Tox. Chem. News, February 9, 1977, p. 25.
10. E. D. Pellizzari, "Analysis of Organic Air Pollutants By Gas Chro-
matography and Mass Spectroscopy", Publication No. EPA-600/2-77-100,
Contract No. 68-02-2262, 112 pp., June, 1977.
11. M. D. Erickson, R. A. Zweidinger, L. C. Michael and E. D. Pellizzari,
Environmental Monitoring Near Industrial Sites: Polychloronaphthalenes,
EPA Contract No. 68-01-178, Task 1, Final Report, 1977, submitted.
12. M. D. Erickson, R. A. Zweidinger and E. D. Pellizzari, "Identification
and Analysis of Polychlorinated Biphenyls and Other Related Chemicals
in Municipal Sewage Sludge Samples", Publication No. 560/6-77-021,
Contract No. 68-01-1978, August, 1977.
33
-------
APPENDIX A
DESCRIPTION OF MASS SPECTROMETERS USED IN THIS PROGRAM
34
-------
FINNIGAN 3300 GC/MS WITH PDF/12 COMPUTER
The Finnigan 3300 mass spectrometer has a mass range of 1000, with
unit resolution over the entire range. Calibration of the system is routinely
performed with PC-43 for lower mass ranges and tris(perfluoroheptyl)-a-
triazine in the higher ranges.
The PDP/12 computer is on-line with the Finnigan system. Long term
storage of data is on L1NC tapes or removable disc packs. The computer can
subsequently treat stored data in several different ways to facilitate in-
terpretation: (a) a reconstructed gas chromatogram is routinely made to
obtain retention times; scan number for a given gas chromatographic peak is
obtained by operator interaction with a CRT display; (b) any given mass
spectrum or an entire series of scans are corrected for background signal
(column bleed, septum bleed, etc.); (c) plots of intensities of specific
ions (mass fragmentography) are made from the scan data. This type of
information is often useful, when correlated with retention time data, for
simplifying the identification of particular compounds. Peak areas are
also readily obtainable from these mass chromatograms and can be used to
provide quantitative information; (d) normalized mass spectra are plotted,
using different types of normalization or amplification factors in order to
facilitate identification; (e) hard copy output of normalized data in
digital form, with various forms of background correction, is also avail-
able.
The GC system in use on the Finnigan mass spectrometer is a Finnigan
9500.
The basic hardware of the POP/12 consists of an 8K central processor
fitted with a teletype, random access disc, CRT display and electrostatic
printer/plotter. The interface to the mass spectrometer was custom-
designed and built and consists of both analog to digital as well as digital
to analog interfaces. The latter involves several unique concepts in
interface design, since by using this system it is possible to put the
entire mass spectral scanning operation under computer control. Since the
data acquisition phase of the spectrometer operation is controlled entirely
by the computer, a large number of different types of acquisition protocols
have been implemented. For example, in the multiple ion detection mode, up
35
-------
up to nine individual peaks can be selected within the entire mass spectral
range, and acquired for varying time intervals as selected by the operator.
In the repetitive scanning mode, scan intervals down to one scan per second
are possible with entire scans recorded either on LINC tapes or disc.
All data processing operations are carried out interactively by means
of programs stored on the small computer.
AEI MODEL 902 HIGH RESOLUTION MASS SPECTROMETER
The spectrometer is equipped with computerized data acquisition and
direct-line access to the Triangle Universities Computation Center (TUCC).
The PDP/8 computer on this mass spectrometer is fitted with a teletype,
high speed paper tape reader and punch, and random access disc. The mass
spectrometer interface is of conventional design, making use of a 15 kHz
A/D converter, which is suitable for high resolution data acquisition.
Mass spectra are acquired at high resolution with on-line data reduction
to the level of peak intensities and peak times. This information is
stored on the disc. Under usual operating conditions, a number of spectra
are accumulated on the disc and then are sent en masse to the Triangle
Universities Computation Center (TUCC) IBM 370/165 for all further processing.
The data are transmitted to TUCC by means of a program specially designed
and executed at CLS. The technique employed involves having the PDP/8
simulate an IBM 2780 card reader which is interfaced by a synchronous 2000
Baud modem to the telephone line. The communication protocol employed is
standard IBM bi-synchronous communication with the PDP/8 carrying out the
entire protocol by suitable software. Once received at TUCC, the data are
processed by means of programs developed at CLS, and reports either returned
to the laboratory or sent out as required to any of the many terminals
located in the TUCC facility.
36
-------
APPENDIX B
TIC CHROMATOGRAM AND REPRESENTATIVE MASS SPECTRA
OF GAS CHROMATOGRAPHIC/MASS SPECTROMETRIC
ANALYSIS OF SAMPLE NUMBER 6077
37
-------
oo
IOO.O-)
00.0-
CO
g 60.0
4J
40.0-
20.0-
.0-
10
Time (min)
- TIC-l- I
Figure B-l. TIC chromatogram of sample number 6077,
-------
BACK-7
rt
CO
100-
30-
80-
ro-
bO-
50-
40-
30-
20-
18-
00-
^^_^lLl^
''""I r..,....|....,--|-'-M'»1
^^..,,._|,^-p.,
.100
U)
VO
4)
P^
88-
70-
68-
50-
40-
38-
20-
10
^^^
e
500
m/e
Figure B-2. Mass spectrum of dlbromobenzene (MW=236) and tetrabroinoethylene
-------
encK-43
H
a
4J
4J
u
£
100-
M
90-
en-
70-
60
50-
40-
30-
20-
10-
-'
2
180-
98-
60-
60-
50-
40-
38-
20-
10-
60-
0
II * 1 1 LlL.lllllllll f* * 1
200 3'H) 300 JOO
'
450
m/e
Figure B-3. Mass spectrum of
(MW=329).
-------
oncx-49
100-
90-
80-
?0-
co
50-
40-
>* 3U-
IJ
To 20-
a
3 ie
Hnn-
vv
*J 2
a
0)
u
u
al ieo1
PH
90-
80-
?0-
60-
50-
48-
30-
20-
10-
60-
,
I
I
| || J| | t , |( | ( i|(| ( |||( _ (
250 3llO 350 -4QO
"1 ! "<' H|»m MHIMI"|I IM |....|..M|.l.l|....pl..|...l|l.l'|l...|-l"|l'"| .|..,.|. till.. iimi|.TT^nn|iMi|.in|. ..!.. |.l.. ,l.l. !.,,! rr~T«-T^
50
m/e
Figure B-4. Mass spectrum of tetrabromobenzene (MW=394).
-------
enrK-121
*»
ro
1?
H
s
0)
3
Percent
100-
90-
BO-
ro-
60-
50-
40-
30-
20-
10-
nn-
uu
2
100-
90-
RO-
70-
60-
50-
48-
30-
20-
10-
j ,^
0
. ll I ,., u- lit!
-., I..J.....I.J.! i.-.i ., . , , , ...,...-! . ........j..... J.........J....,....! ( ..._(_ .......(. .... ii|i..it«
250 3l\8 350 ' 1
-------
pncK-no
s
Jl
,111
31
llllllllll.lv,,,,!.,.,^,-*
350
100
r T
M >00n
*> 01
U) PM 90-
00-
70-
60-
50-
40-
38-
20-
10-
nn-
vu
1
1 1 '" " " 1 1 1 "I"
1
1
III
| 1, , , .-.., , (...v-, - -. - -, , , , , --,-
"I"""T
400
5'..0
m/e
Figure B-6. Mass spectrum of C
-------
K I 4-I-
100-i
90
ao-
70-
60-
50-
40-
30-
4J 20H
.0-
00-
250
.._-
350
O lOO-i
M
98-
80-
70-
60-
50-
40-
30-
20-
10-
oo-U-r
450
|llll|l^
^T" 1
500
m/e
'""I ,....,.p"i-|-i|.-!-
600
Figure B-7. Mass spectrum of hexabromobenzene (MW=552).
-------
inn-
90-
00-
ro-
60-
50-
40-
3 20-
CD
§ I0
fl 00-V
H 20C
Percent
(fi c
o o
eo-
ro-
60-
50-
40
30-
20-
10-
00-
1
)
""I
1 1
,J|Lill
1
1
II II II 1 1 1 1
LJII ^,iu III, Jill III II
2 o 360 alo
...,,.> |,|l IIII||.,....|J|IIII ( ,.,,., , ,iiii|, .,,!,,., , ,
lio 500 'jOO
m/e
Figure B-8. Mass spectrum of tetrabroraobiphenyl (h«J=A70) andxC. _H,Dr.O (MW=/i86).
12 O 4
-------
nncr-iv
600
650
7W rin
O ,00-
(2J 3H-
00-
70-
60-
50-
40-
30-
20-
10
00
800
850
m/e
"""'I I I I I""""
950
Figure B-9. Mass spectrum of pentabromobiphenyl (MW=5A9) and
(MW=565)
-------
»:- r.
^
4J
Intensd
i
Cl
«
100-
co
ro-
30
20-
11.-
00-
5
HI nun 1 1
0 600
bso 700 . rr."
100-
90-
eo-
7f-
60-
50-
40-
36-
20-
10-
an
,
GOO 85U nnn oio
ra/e
Figure B-10. Mass spectrum of hexabromobiphenyl (MW=628) and C-.H.Br.O (MW=64A).
12 4 6
-------
00
4J
H
g
8
I
Percent
100-
90-
80-
.'0-
60-
50-
40-
30-
20
10-
5
100-
90-
80-
70-
60-
50-
40-
30-
20-
10-
00-
lILlJ
i tif«*«n
u
III
II ll
600
,
III 1
6SO 701) 7'iu
,
0110 BOO
m/e
Figure B-ll. Mass spectrum of heptabromobiphenyl (MW=707) and C.-^H-B^O (MW=723)
-------
vo
It'll'
HI
;.i> .
Jti
311
* "
S i
I 00
3
o
100
00
ro
60-
50-
30
20-
10
I.JM
bOO
!*TW. 1II11111111111(111111 II i |r
650
lulu r
000 85U
701)
ot'n pdo
m/e
Figure B-12. Mass spectrum of octabromobiphenyl (MW=786) and c12n2Br8°
-------
. -i
11II)-I
§
80-
.ii
60-
50
40-
70-
20-
-
ou-
luJl
Ui
o
o
M
o)
PU
100-
90-
80-
ro-
60-
50-
40-
20-
10-
00-
,1
LJ
il i
I rill
il ill II 'I' 'I
oflo
850
*y»^^»*T^yTT*|»T»TTTT««i
900
m/e
|*»»*|
«bll
Figure B-13. Mass spectrum of nonabromobiphenyl (MW=866) and C12HBr90 (MW=881).
-------
rm.i
inn-,
rnu
£
Intensd
4J
S
o
M
0)
P*
1 1 lit -
»*r» -
en
i'n-
tu-
50-
40-
70-
:o-
10-
00-
100-
90-
w-
ro-
f.O-
30-
20-
ICi-
,. ,i.i-4 Jill
r.id
ill
l..^.tll|-.ttt.l..l.t. .1. I..HI..JH I.I 1
.ili>iii
050
.... ,..^
rno
LttHfl.UjtLll
gnn
ti
kf*»K*
m/e
Figure B-14. Mass spectrum of decabromobiphenyl
-------
rnri:
mo-
no-
ro-
50-
JU
30
20
oo
.........
500
61)0
,-ut)
Ul
ls>
0) 90
P-I
60-
60-
50-
40-
30-
20-
10-
00-U^.|lU4'luJK4lA<
rie
|IUi|UiJl|...l,.'.'|'.t.|...i|Mlut.jiJ.
ado
.l.p.^^,.llJ1llll,4ll|l|lll,U4.1llll|m|,mT.,,r ,^.J|ll!l|
m/e
Figure B-15. Mass spectrum of c12BrlO°
-------
APPENDIX C
REPRESENTATIVE MASS SPECTRA OF DECABROMOBIPHENYL ETHER AND IMPURITIES
53
-------
Ut
100 i
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
00
650
600
650
700
850
900
950
750 800
m/e
Figure C-l. Representative mass spectrum of decabromobiphenyl ether C _Brin
(m/e 960) and C12BrgClO (m/e - 914) which co-elute.
-------
100
90 -
80 .
70 .
60 .
60
Ui
40
30
20 -
10
00
ILu
I 'I 'I
550 600
' I | ' I' n I ' I T* i' > ' I ' I' | ' i 11 '!"»'111 U i I ' < ' i ' 1 ' I 111
650 700 750 800 850 900 950
in/i
Figure C-2. Mass spectrum of C12Brg110 (m/e = 880) found in DECADROM-DW sample.
-------
ui
100 -
80 .
60 .
40 -
20 -
00
8
£
550
100 ,
80 -
60
40
20 .
00
800
I
600
650
700
1 ^
750
850
900
950
m/e
Figure C-3. Mass spectrum of C.-BrgH-O (m/e = 802) found in DECABROM-DW sample.
Note: Trace amount of sample approaching the digitization level.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
1-560/6-77-020
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Analysis of a Series of Samples for Polybrominated
Biphenyls (PBBs)
6. REPORT DATE
Prepared August. 1977
8. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
M. D. Erickson, R. A. Zweidinger and E. D. Pellizzari
a. PERFORMING ORGANIZATION REPORT NO.
Task V Final Report
9. PERFORMING ORGANIZATION NAME ANO ADDRESS
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-1978
12. SPONSORING AGENCY NAME ANO ADDRESS
Office of Toxic Substances
U. S. Environmental Protection Agency
Washington, D. C. 20460
13. TYPE OF REPORT ANO PERIOD COVERED
Final March 10 - June 18. 1977
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Methods for the analysis of polybrominated biphenyls (PBBs) by gas chromatog-
raphy/ mass spectrometry/computer (GC/MS/COMP) were developed using a 45 cm x 0.2
cm i.d. glass column packed with 2% OV-101 coated on Gas-Chrom Q. The column was
programmed from 150-300°C at 20°C/min for the chromatography of mono- through
pentabromobiphenyl and from 220-300°C at 12°C/min for hexa- through decabromo-
biphenyl. Two separate analyses were required to adequately separate the lower
isomers and to yield definitive peaks for the higher isomers. A total of 80
samples were analyzed by GC/MS in the Multiple Ion Detection (MID) mode. They
contained from undetectable to 860 Ug/ml of PBBs. The higher isomers accounted
for the majority of the PBBs found. Mass spectra obtained during GC/MS analysis
of some of the more highly concentrated samples not only confirmed the presence
of PBBs, but also detected polybrominated biphenyl ethers and other brominated
compounds.
Three commercial samples of decabromobiphenyl ether (C^Br^O) were analyzed
for impurities by GC/MS using the same conditions as for the higher PBBs. All
three samples contained Ci^B^ClO in small amounts and one sample contained
traces of Ci2H2Br80 and Cl2HBrgO.
17.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Polybrominated Biphenyls
PBBs
GC/MS
Decabromobiphenyl ether
Brominated organics
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (ThisReport)
unclassified
21. NO. Or PAGES
69
20. SECURITY CLASS (This page)
unclassified
22. PRICE
EPA Poem 2220-1 (R««. 4-77) PMKVIOUS COITION is OBSOLETE
-------
INSTRUCTIONS
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