FINAL REPORT
GC-MS INVESTIGATION OF SEDIMENT
AND PLANT EXTRACTS FOR PCB's
Submitted To:
ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL RESEARCH LABORATORY
CORVALLIS, OREGON
nn
x
Submitted By:
~ NORTHROP SERVICES, INC.
ENVIRONMENTAL SCIENCES GROUP
200 S.W. 35th STREET
CORVALLIS, OREGON 97330
II
~
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FINAL REPORT
GC-MS INVESTIGATION OF SEDIMENT
AND PLANT EXTRACTS FOR PCB's
NSI-CORVALLIS: 79-07
Randy McRobbie
May 11, 1979
Under Contract No. 6fi-n3-2fi5n
Walter F. Burns
Scientist
Northrop Services, Inc.
Submitted by:
| jn Approved by:/
William Griffis, Chief
Terrestrial Systems
Analytical Services
Corvallis Environmental
Research Laboratory
Nelson M. Pettit
Program Manager
Northrop Services, I
D. F. Krawczyk, Di/ector
Terrestrial Systems
Analytical Services
Corvallis Environmental
Research Laboratory
-------
GC-MS Investigation of Sediment
and Plant Extracts for PCB's
INTRODUCTION
Extracts of sediment and plant tissue samples were supplied by Analytical
Support Staff. Electron capture gas chromatography had revealed compounds
with similar retention times to polychlorinated biphenyls (PCB's). Selected
ion monitoring (SIM) gas chromatography-mass spectrometry was performed as a
specific mass detector on Aroclor 1254 and Aroclor 1260 since these were
thought to contain the major PCB's present. A "most likely Aroclor formu-
lation" was determined based on matching relative retention times of the PCB's
in the sample to those in the standards.
EXPERIMENTAL
The Finnigan Model 3200 mass spectrometer with a modified Varian 1400 gas
chromatograph, single stage glass jet separator interface, and a PDP 8/E
computer with hard disk storage were used for the analysis. All plots were
generated using a Houston Instruments C0MPL0T digital plotter.
Electron impact mass spectrometer conditions were as follows: electron
energy 70 eV; ion energy 5.8 V; sensitivity 10-8 amps/V; and electron multi-
plier 2304 V.
SIM scans were conducted using the masses 246(DDE), 294(4 CI), 330(5 CI),
363(6 CI), and 394 (7 CI) where the numbers in parentheses are the numbers of
chlorines per biphenyl molecule. Integration times were 200 msec/amu for DDE
and 750 msec/amu for the PCB's. The computer software PLTSIM/PTSMPT was also
used in special cases to detect PCB's with lower degrees of chlorination.
-------
A total ion current scan was requested and performed on sample 2937020
using a mass range of 45-250 and 251-450 amu with 7 and 10 msec integration
times respectively to confirm the presence of PCB's by a second method. The
chlorine isotopic substitution pattern was used to determine the number of
chlorines per biphenyol molecule.
The chromatographic column was a 1.8 m X 4 mm ID glass coil packed with
4% SE 30-6% 0V210 on 100/120 GasChrom Q. High purity helium passed through a
HydroPurge filter with a flow rate of 23 mls/m1n was used as the carrier gas.
1,l-Dichloro-2,2-bis(p-chlorophenyl) ethylene (p.p'-DDE) was added to each of
the samples and standards as an internal reference for the calculation of peak
relative retention times (RRT's). p.p'-DDE was selected for the internal
reference material because it has no fragments that interfere with single ion
monitoring of PCB's, it has a fragment at m/e 246, no PCB's have fragments to
interfere, and it has a retention time similar to the PCB's.
DISCUSSION
Table 1 shows the relative retention times (RRT's) of the peaks in four
Aroclor 1254 runs compared to p.p'-DDE. It can be seen that the RRT's are
good for corresponding peaks. These data were collected on four different
days spanning the duration of sample investigation. Only one run of Aroclor
1260 was made, and these data are presented in Table 2. The RRT's are very
similar to those generated by Webb and McCall. The mass fragmentograms for
the Aroclor 1254 runs are shown on Appendix pages 1A-5A. The fragmentograms
for Aroclor 1260 are shown on pages 6A-7A.
Table 3 1s a comparison of the retention times of the samples to those of
Aroclor 1254 and 1260. It 1s apparent that all samples contain some PCB
-------
Isomers. Sample 2937008 shows a particularly good match to Aroclor 1254. The
absence of some chlorobiphenyls in environmental samples can be expected due
to selective partitioning between soil and water or lipids and water (Tulp and
Hutzinger, 1978) (Paulou and Dexter, 1979). Sample 2937024 1s interesting in
that it contains a large number of chlorobiphenyls. Some of the isomers have
retention times corresponding to the PCB's in Aroclor 1260 (Table 3) but some
isomers present in Aroclor 1260 are not found in the samples. The fragmento-
grams for the 5 samples are found on pages 8A-12A
In addition, SIM searches for lower chlorinated biphenyls were conducted
on samples 2937024 and 2937020 using PLISIM/PRSMPT. Sample 2937020 shows at
least 5 dichloro biphenyls (m/e 224) 5 trichlorobiphenyls (m/e 260), and 4
tetachlorobiphenyls (m/e 294). Sample 2937024 contains 3 monochloro isomers
(m/e 190), 7 dichloro biphenyls, at least 7 trichlorobiphenyls, and at least 5
major tetrachlorobiphenyls. The fragmentograms are found on pages 13A-16A.
The presence of these low chlorination products suggest two possibilities: 1)
dechlorination of higher chlorine content biphenyls by metabolic or photolytic
means, or 2) presence of some other Aroclor formulation of lower average
percent chlorine such as Aroclor 1242 or Aroclor 1248.
A total ion current scan was run on sample 2937020. The reconstructed
gas chromatogram is on page 17A. The numbers above the peaks indicate the
number of chlorines per biphenyl molecule. This is determined through the
chlorine isotopic substitution pattern of the molecular ion (see McRdbble,
1979 for explanation). The mass spectra or partial mass spectra for the
individual peaks are found on pages 18A-32A. It 1s possible to calculate the
percentage composition of a complex peak by summing the intensities of the
Ions at the molecular ion and the M*-35 peaks for the compounds (Webb and
-------
McCall, 1973). In performing this calculation for spectrum 90-77, a mixture
of trichloro- and tetrachlorobiphenyls yields 69% tetrachloro and 31% trichlor-
obiphenyls. The mass spectrum of the peak and data used for this calculation
are found on page 33A.
A summary of the most likely Aroclors contained in the 5 samples is
presented in Table 4. All the samples have PCB's with similar retention times
to those in Aroclor 1254, and two samples correspond well with Aroclor 1260.
Three of the samples also have lower chlorinated biphenyls indicative of some
lower series.
SUMMARY
In conclusion, specific mass detection using the mass spectrometer and
comparison of relative retention times with a known standard appears to be an
excellent method for detecting and confirming polychlorinated biphenyls. The
advantages are excellent specificity and ease of data interpretation. Confir-
mation of biphenyl content can be achieved by total ion current scans on the
mass spectrometer. The primary limitation, of course, is the lower sensitivity
of the mass spectrometer compared to the electron capture detector. The method
does appear to be very useful, however, if the samples can be concentrated to
the detection range of the mass spectrometer.
-------
Table 1. Retention Times of PCB's in Replicate Aroclor 1254 Standard Runs
Peak*
RRT It
RRT 2
RRT 3
RRT 4
Ave,
ODE
100
100
100
100
100
294-1
45
44
47
44
45
294-2
51
51
54
51
52
294-3
54
55
58
55
56
294-4
69
68
70
68
69
294-5
78
79
84
79
80
330-1
67
--
70
65
67
330-2
81
78
84
81
81
330-3
96
96
98
96
96
330-4
105
102
104
104
104
330-5
128
127
125
127
127
330-6
153
153
146
152
151
362-2
121
120
125
118
121
362-3
147
147
146
146
146
362-4
178
179
174
176
177
Peak number appearing at a given m/e value e.g. 294-1 is the first peak
appearing at m/e 294.
t Retention time relative to p,p'-DDE =100 for run #1.
-------
Table 2. Relative Retention Times of PCB's in Aroclor 1260
Peak*
RRTt
Webb & McCall I
DDE
100
100
362-1
98
98
362-2
112
117
362-3
121
125
362-4
147
146
362-5
161
160
362-6
179
174
394-1
153
146
394-2
160
160
394-3
192
203
394-4
234
232
394-5
292
280
Peak number appearing at a given m/e value.
t Retention time relative to p.p'-DDE.
£ Relative retention times found by Webb and McCall, 1973.
-------
Table 3. Comparison of samplle PCB's relative retention times to Aroclor 1254 and 1260. All RRT calculations
are based on p,p'-DDE retention time equals 100. Peak numbers correspond to those shown on the mass fragmentogram
in the Appendix.
SAMPLE
1254 T260 2937008 2937016 2937020 2937024 2937026
ODE
100
100
100
100
100
100
100
m/e
Peak RRT
Peak
RRT
Peak RRT
Peak
RRT
Peak
RRT
Peak
RRT
Peak
RRT
190
6 peaks
3 peaks
224
5 peaks
7 peaks
260
5 peaks
7 peaks
294
1
31
1
30
2
33
1
37
1
37
3
37
2
36
1
45
2
44
1
44
2
44
4
45
3
42
2
52
3
51
2
51
3
52
5
51
4
51
3
56
4
55
3
55
4
56
6
55
5
55
5
64
7
63
4
69
6
69
4
68
8
68
5
80
7
79
9
78
330
1
56
1
67
1
67
1
67
2
68
1
67
2
81
2
80
2
79
3
78
2
77
4
82
5
87
3
96
3
96
4
104
4
105
3
104
6
105
3
101
5
127 .
6
151
362
1
98
1
98
1
96
2
112
2
110
2
110
2
121
3
121
1
121
3
120
3
146
4
147
2
147
4
146
5
161
4
177
6
179
3
178
5
178
394
1
153
1
154
2
160
2
185
3
192
3:
197
4
234
5
292
-------
Table 4. Summary of "most likely" Aroclors contained 1n the samples.
Sample No. Aroclor
2937008 1254
2937016 1254, + some lower 1232 or 1242
2937020 1254, + some lower series
2937024 1254, 1260, + some lower series
2937026 1254, 1260
-------
APPENDIX CONTENTS
Pages Contents
1A-5A Replicate Aroclor 1254 fragmentograms
6A-7A Aroclor 1260 fragmentograms
8A Fragmentograms for sample 2937008
9A Fragmentograms for sample 2937016
10A Fragmentograms for sample 2937020
11A Fragmentograms for sample 2937024
12A Fragmentograms for sample 2937026
13A-14A Low chlorine fragmentograms for 2937020
15A-16A Low chlorine fragmentograms for 2937024
17A TICP for sample 2937020
18A-32A Mass spectra for peaks in 2937020
33A Calculation of fixed PCB's in peak 90-77 2937020
-------
REFERENCES
McRobbie, R. D. Investigation of Polychlorinated Biphenyls in Industrial
Effluents. Report prepared for USEPA. 1979
Paulou, S. P. and R. N. Dexter. Distribution of Polychlorinated Biphenyls
(PCB) in Estuarine Ecosystems. Testing the Concept of Equilibrium Parti-
tioning in the Marine Environment. Environmental Science and Technology.
13 no. 1. 1979
Tulp, M. Th. M. and 0. Hutzinger. Some Thoughts on Aqueous Solubilities and
Partition Coefficients of PCB, and the Mathematical Correlation Between
Bioaccumulation and Physio-Chemical Properties. Chemosphere. no. 10. p
849-860.
Webb, R. G. and Ann C. McCall. Quantative PBC Standards for Electron Capture
Gas Chromatography. Journal of Chromatographic Science. 12 366-373.
-------
Aroclor 1254 Run 1
394
362
330
294
246
Til
250
300
350
200
50
100
150
-------
«« i«- CtilVSF1!. tiff-7' hou.2! Jn;wsi.iototnr 4 .¦«. *y?r;a. ('ixas oiA*r uo.fc-ooo phi.hum* u s a CS&rvlJ^L.^ C" HOUSTON iN5»T««>i4£wr J austm » W
Aroclor 1254 Run 2
394
-T-1
362
i « i » i ' i » i ¦ i ' i ' i ¦ i
i « » ¦ > ¦ i ¦ i « i ' » ¦ i ¦ i ¦ «
TIC
'« «¦ i
i ¦ i « i ' i « i ¦ i « i 1 i ' i ¦ i ¦ i ¦ i 1 i ' i » i ¦ i ' i » i « i « i ' i ¦ i ¦ i » i 1 i ' i
i ¦ i ¦ i » i « i
100 150 200 250 300 :350 400 450
no
>
-------
Aroclor 1254 Run 3
394
362
330
294
246
Til
so
100
ISO
200
2S0
350
300
400
450
SOO
550
GO
3>
-------
Aroclor 1254 Run 4
330
246
trr
200 250
3S0
s3o
SO
550
150
600
650
-------
Aroclor 1254 Run 4
394
362
246
Til
350
630
750
900
50
550
100
100
150
600
250
Ol
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330
Aroclor 1260
¦AA^
246
\
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tbj wr
-nr
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-------
Aroclor 1260
394
362
Til
v.
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ur
w
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Sample 2937008
394
I ' t ¦ I ¦ I ' I »T
t ¦ «-r
"f i f
362
' > i i j^~ i - i
f M ' I ' I"
i « i 1 i " i " i ' i ' r « i 1 r » i » i » i » i 1 i « i ' i 1 i 1 » 1 i ' i ' \
i » i ' i ' i ¦ i ' i » r*
, ,r, r,f r> T r< y..« t.f 1- | » |» M i m ¦ I ' I
,1 ,.1 ¦ -f ,-T MT || r I f l | » I ¦ I > I > I <" I »' I ¦ 1 ¦ I » I > I I I ¦' I % f I' I »¦ ! M-t
Til
r ¦ ¦ ¦ i ' i1 ¦ i *¦ t * i ¦« i « i ¦ » « i » i ¦ i « i » i « i « i » i """i ' % i ¦ i » » ¦ i « i * i » i » i « i » i ¦11 * i « i * i ' i ' i * i * i ' i ¦ i « i ' i ¦ i ' i * t
50 100 150 200 250 300 350 400 45
§
-------
Sample 2937016
394
362
330
294
246
V
Til
50
100
150
200
250
300
vo
-------
Sample 2937020
394
| mt\Hu " I ^ 1
362
*»»*» s
294
246
Til
SO
aJV^v
100
ISO
200
250
300
350
7400
450
500
5S0
o
y*
-------
Sample 2937024
394
362
330
294
246
Til
250
450
SOO
100
400
5
SO
ISO
200
-------
Sample 2937026
394
362
330
294
246
w»v»
Til
50
100
150
200
250
350
300
400
ro
-------
SRMO.E 2937020 DOG SPIKE SE30-0V210 F38 6 1973
13A
B-
I'll 1111| ij M i|i|i 11) MM 11 M M
163
1S0
203
1111111 Ml1111111
2S0 330
-------
SFMBLE 2337329 DDE SPIKE JE39-0V210 FSB 6 1373
14A
-------
15A
SRhPLE 2937021 SIM S0RRCH FOR LOW CHLORINES 1-12-73
-------
SfiMPLE 2337021 SIM S&RRCH FDR LOW CRXBINES 1-12-73
16A
sea
291
8
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8
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Tm 111111 I-Im ¦ I il 'I 'Ml'
0 S3 1C3 1S3 283
iTT'Tifi'l ''I'1
2SI3 333
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TOTPL ION CURRENT 9RHPLE 2337020 SE3EHJV210 F3B 8 73
8
SPECTHLM NICER
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TIC 20
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150
200
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200
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SPECTHJh MLMBER 62 - S7
TOTHL ION CURRENT SflMPLE 2337020 SE3HJV210 FSB 8 73
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SPECTFU1 NUMBER 67 - S7
TOTFL ION CURRENT SPM=LE 2337820 SE30-CJV210 F3B 8 79
8.
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mil vi if mi
100 110 120 130 110 159 160 170 160 190 200 210 220 230 210 250 260 270 200 290
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SPECTHH NLMBER 70 - S7
TOTPL ION CURRENT 9fW£ 2337028 SE30-0V21S F3B B 73
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100 110 120 130 110 ISO 160 170 100 130 200 210 220 230 210 2S0 260 270 '
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SPECIHJM NIGER 63 - 77
TOTFL ION CURRENT SAMPLE 2337020 SE30-0V210 F3B 8 79
fll hn«j L|lill!!li|l J |ta*J 111! n..jlllll]l,tiPn
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MS E
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SPECTFIH NUMBER 86 - 77
g TOIHL ION CURRENT SMPLE 2937020 SESWJV210 FSB 8 79
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SPECTFUH NLHBER 30 - 77
g TO1PL ION CUPREHT SFMPLE 2337020 SE30-CW210 F3B 8 73
8.
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30 W SO 60 70 80 39 100 110 129 130
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ISO 160 170 190 130 200 210 220 230 210 2S0 260 270 200 295 3E
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8
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SFEC1HJM NUT«R 111 - 101
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30 10 SO 0 70
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SPECTRUM NLMBER 126 - 121
TOTAL ION CLPRENT 3RMPLE 2337020 SE30-CV210 F3B 8 73
g
299 399
i|uih
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TIC20
100
SCAN
80-
60-
40-
20-
i ¦ i i
200
250
135
-------
TIC20
100
80-
60-
40-
20-
$C AN
200
250
165
2
I
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300
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80-
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200
I ' I
250
2
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100
80-
60
40-
20-
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200
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250
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251
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300
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SPECTRUM NLTfiER 30 - 77
TOUL 1(N CURRENT SflHPLE 2337820 SE3O-OV210 F3B 8 79
W
4*3 units
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