United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
Las Vegas NV89114
Research and Development
EPA-600/S4-84-068 Sept. 1984
Project Summary
Fused Silica Capillary Column
GC/MS Quality Control Protocol
for the Determination of Semi-
volatile Priority Pollutants
Viorica Lopez-Avila
This quality control protocol is
intended to serve as a reference docu-
ment for those laboratories employing
fused silica capillary column (FSCC)
gas chromatographic/mass spectro-
metric (GC/MS) techniques for the
analysis of the extractable semivolatile
priority pollutants in all environmental
matrices. The document presents ap-
paratus requirements and gives guid-
ance for standards preparation, as well
as instrument setup and calibration.
Reference information, including inter-
nal standard assignment, quantitation
mass, relative retention times (RRT)
values, interlaboratory and intralabora-
tory response factor (RF) values, is also
presented. This document provides a
schedule for GC/MS system calibra-
tion requirements including ion abun-
dance calibration, column performance
testing, sensitivity verification, system
linearity, and injection technique repro-
ducibility.
This protocol does not provide guid-
ance regarding sample extraction and
workup; therefore, any quality control
(QC) parameters related to this aspect
of the analysis are not addressed in this
protocol.
This Project Summary was developed
by EPA's Environmental Monitoring
Systems Laboratory, Las Vegas. NV. to
announce key findings of the research
project that is full documented in a sep-
arate report of the same title (see Project
Report ordering information at back).
Introduction
Fused Silica Capillary Column (FSCC)
Gas Chromatography/Mass Spectro-
metry (GC/MS) has been shown to
provide an effective instrumental analy-
sis configuration for the determination of
semivolatile priority pollutants in extracts
of environmental samples and hazardous
wastes. FSCC GC/MS is employed by
various EPA programs in classifying
materials as hazardous/non-hazardous
for organic compounds of regulatory
interest.
The protocol will give the user guidance
for instrument setup and calibration, as
well as criteria to assess data quality.
These criteria were established based on
interlaboratory and intralaboratory evalu-
ation of this protocol.
The QC requirements described in this
document fall into three groups:
e QC requirements during the initial-
ization process
C QC requirements during sample
analysis
O QC requirements during ongoing
calibration
Initialization Process
The initialization process includes the
analysis of the system performance
standard and three composite priority
pollutant standards (concentrations 20,
100, 200, fjg/mL). The system perform-
ance standard: (1) demonstrates ion
abundance calibration criteria, via deca-
fluorotriphenylphosphine (DFTPP) at 50
ng, (2) provides information regarding
system linearity, and (3) demonstrates
the ability to chromatograph acidic and
basic compounds. The composite priority
pollutant standards are analyzed only
after the QC requirements for the system
performance standard are met. Response
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factors for the composite mixture of
phenol, naphthalene, anthracene, chry-
sene, and benzo(a)pyrene are utilized as
the principal indicator of data acceptabili-
ty.
Sample Analysis
Sample analysis begins after the
initialization criteria are met. During
sample analysis, the absolute areas of the
quantitation ions of the five internal
standards (phenol-ds, naphthalene-da,
anthracene-dio, chrysene-di2, and ben-
zo(a)pyrene-di2> are monitored.
Ongoing Calibration
Ongoing calibration requires that after
8 hours of data acquisition, the system
performance standard and a single level
calibration standard a re analyzed to verify
system performance. One week after the
first initialization procedure and after any
maintenance is performed on the system,
the initialization procedure must be
repeated.
Results
This protocol was tested in an interlab-
oratory study; the precision/distribution
of RF values observed is shown in Figure
1. When these interlaboratory RF values
(as shown in Tables 1 and 1 a) were com-
pared to those obtained on a triple quad-
rupole mass spectrometer, 74 percent of
the electron impact GC/MS response
factors (RF) determined for 53 extractable
priority pollutants were found to be with-
in ±15 percent of values determined in
the independent interlaboratory single
quadrupole GC/MS study. The precision
of RF determinations for 53 extractable
priority pollutants (mean relative stan-
dard deviation 11.9 percent) was found to
be similar to that previously observed for
routine GC/MS multianalyte RF determi-
nations.
Response factors may be viewed as
constants to be utilized in the internal
standard quantitative analysis of organic
compounds by electron impact GC/MS in
environmental analysis. For comparable
injected weights, the response factor of
an analyte is simply a ratio of the ion
current "area" of analyte and internal
standard at their respective quantitation
m/z values. A series of multianalyte,
multilevel response factor precision
determinations can be considered as a
measure of the relative sensitivity and
stability of a given instrument and, hence,
its quantitative capabilities. Response
factor monitoring is an important mecha-
Analyte
N-Nitrosodimethylamine
Bis/2-ch/oroethy/jether
2-Chlorophenol
Phenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1.2-Dichlorobenzene
Bis(2 - chloroisoprop yl)ether
Ethane, hexachloro-
N-nitroso-di-N-propylamine
Nitrobenzene
Isophorone
2-Nitrophenol
2.4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-M-cresol
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2-Chloronaphthalene
Acenaphthytene
Dimethyl phthalate
2,6-Dinitrotoluene
Acenaphthene
2,4-Dinitrophenol
2,4-Dinitrotoluene
4-Nitrophenol
Fluorene
4-Chlorophenyl phenylether
Diethyl Phthalate
4,6-Dinitro-O-cresol
Diphenylamine
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Dibutyl phthalate
Fluoranthene
Pyrene
Benzidine
Butyl benzyl phthalate
Bcnz(ajanthracene
Chrysene
3,3^-Dichlorobenzidine
Bis!2-Ethylhexy)phthalate
Di-N octyl phthalate
Benzofa/pyrene
Dibenzofa,h)anthracene
Benzofghijperylene
Figure 1. Interlaboratory (4
Response Factor, RSD
25 50
75
i
i
i
I
I
i
~j
i
I
i
1
i
i
L
i
i
1
i
I
r
r
i
nr 1 ft nn/
i
j
r~
Lab) response factor relative standard deviation.
-------
Table 1. Intralaboratory Response Factors of Semivolatile Priority Pollutants
Split/ess
Injection
Compound
N-Nitrosodimethylamine
B/s(2 - chloroeth yljether
2-Chlorophenol
Phenol
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
Bis(2-chloroisopropyl)ether
Hexachloroethane
N-Nitroso-di-n-propylamine
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Bis(2-chloroethoxy)methane
2,4-Dichlorophenol
1 ,2,4- Jrichlorobenzene
Naphthalene
Hexachlorobutadiene
4-Chloro-3-cresol
Hexachlorocyclopentadiene
2,4,6-Trichlorophenol
2-Chloronaphthalene
Acenaphthylene
Dimethyl phthalate
2,6-Dinitrotoluene
Acenaphthene
2,4-Dinitrophenol
2,4-Dinitrotoluene
4-Nitrophenol
Fluorene
4-Chlorophenyl phenylether
Diethyl Phthalate
4,6-Dinitro-2-cresol
Diphenylamine
Azobenzene
4-Bromophenyl phenyl ether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Benzidine
Butylbenzylphthalate
Benzfa)anthracene
Chrysene
3,3-Dichlorobenzidine
Bis(2-ethylhexyl)phthalate
Di-n-octyl phthalate
Benzofj+kjfluoranthenes
Benzo(a)pyrene
Indenof1,2,3-cd)pyrene
Dibenzo(a, h)anthracene
Benzofghilperylene
PFa
0.72
0.96
0.73
1.16
0.66
0.85
0.72
0.26
0.35
0.055
0.18
0.89
0.23
0.30
0.53
0.29
0.30
1.01
0.12
0.29
0.15
0.21
0.64
0.88
0.73
0.18
0.61
0.083
0.23
0.18
0.77
0.38
0.82
0.14
0.52
...
0.21
0.24
0.14
1.06
1.07
1.44
1.10
1.13
0.15
0.67
1.04
1.02
0.31
1.07
1.70
...
0.88
..-
0.60
0.65
RSD
24.5
3.0
4.0
2.8
0.9
3.8
3.5
7.9
8.2
3.8
0
1.7
6.7
3.3
1.9
0
1.9
6.5
0
2.0
7.5
5.4
2.4
4.3
3.1
6.3
5.0
38.3
11.1
8.3
7.8
4.1
4.6
16.9
4.0
...
4.8
4.2
7.1
1.4
8.0
9.6
6.6
2.8
24.7
10.8
2.4
6.1
0
3.9
5.4
...
2.3
...
2.5
8.6
On-Column Injection
flfa
...
1.078
1.001
1.335
0.886
1.090
0.942
0.232
0.428
0.092
0.251
0.810
0.326
0.367
0.541
0.388
0.418
1.089
0.188
0.383
0.259
0.313
0.814
0.994
1.018
0.275
0.757
0.166
0.325
0.207
0.866
0.524
1.018
0.219
0.587
0.069
0.308
0.339
0.205
1.221
1.045
1.428
1.201
1.160
...
0.698
1.043
0.878
...
1.012
1.347
...
0.961
...
0.784
0.815
FISD
...
11.4
9.2
S3
9.5
12.3
12.8
6.9
9.0
7.7
4.4
14.7
1.4
5.6
3.8
4.4
5.8
19.2
5.4
7.2
6.9
7.7
6.1
6.5
4.1
7.4
20.0
16.8
2.5
17.0
15.6
10.7
14.9
11.0
8.0
19.1
5.0
5.7
10.4
7.2
25.0
22.3
12.4
6.4
...
19.2
5.0
21.1
...
21.7
20.4
...
21.3
...
17.3
15.3
RRT
...
0.988
0.994
1.002
1.065
1.106
1.235
1.389
1.455
0.725
0.750
0.852
0.872
0.940
0.964
0.980
0.992
1.008
1.093
1.297
1.377
1.425
1.466
1.626
1.656
1.671
0.745
0.768
0.795
0.806
0.833
0.843
0.849
0.863
0.870
0.870
0.926
0.941
0.931
0.996
1.003
1.136
1.202
1.237
b
0.957
0.998
1.002
b
1.037
1.108
b
1.002
b
1.153
1.185
RSD
...
0.2
0.2
0.3
0.7
0.6
1.0
1.3
1.5
0.8
0.4
0.6
0.3
0.3
0.2
0.7
0.1
0.1
0.3
0.3
0.3
0.3
0.3
0.3
0.2
0.2
0.0
0.2
0.2
0.7
0.7
0.7
0.7
0.3
0.7
0.7
0.7
0.7
0.7
0.7
0.1
0.1
0.1
0.1
b
0.1
0.1
0.1
b
0.1
0.1
b
0.1
b
0.2
0.3
'Number of determinations is 3 for split/ess injection and 7 for on-column injection.
^Compound not present in the standard.
nism in establishing and maintaining
control of multilaboratory programs that
routinely employ GO/MS for the qualita-
tive and quantitative analysis of organic
compounds.
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Table 1a. Intralaboratory Response Factors of Pesticides
Split/ess
Inject/on
Compound
Alpha-BHC
Gamma-BHC
Beta-BHC
Delta-BHC
Heptachlor
Aldrin
4.4'-DDE
Dieldrin
4,4' -ODD
4.4'-DDT
Beta Endosulfan
Endosulfan sulfate
Endrin
Alpha endosulfan
Heptachlor epoxide
RF"
0.143
0.154
0.188
0.103
0.089
...
0.243
0.292
0.458
0.346
0.039
...
0.082
0.034
0.059
RSD
9.1
13.7
28.4
6.2
10.9
...
14.8
23.3
12.1
8.6
7.4
...
28.6
5.6
6.2
On-Column Injection
RF*
0.169
0.269
0.247
0.127
0.143
...
0.246
0.204
0.476
0.433
0.041
0.089
0.076
0.036
0.077
FISD
7.0
9.2
24.3
5.0
9.5
...
8.7
5.0
6.0
5.8
7.1
12.0
10.8
5.2
8.5
RRT"
0.931
0.982
1.024
1.024
1.087
...
0.883
0.880
0.923
0.957
0.910
...
0.880
0.855
1.196
FtSD
0.1
0.1
0.1
0.1
0.2
...
0.1
0.1
0.1
0.1
0.1
...
0.1
0.1
0.2
"Number of determinations is 3 for sp/itless injection and 7 for on-column injection.
Viorica Lopez-Avila is with Acurex Corporation. Mountain View, CA 94039.
Andrew D. Sauter was the EPA Project Officer (see below for present contact).
The complete report, entitled "Fused Silica Capillary Column GC/MS Quality
Control Protocol for the Determination of Semivolatile Priority Pollutants,"
(Order No. PB 84-224 674; Cost: $10.00, subject to change) will be available
only from:
National Technical Information Service
5285 Port Royal Road
Springfield. VA 22161
Telephone: 703-487-4650
For information Leon D. Betowski can be contacted at:
Environmental Monitoring Systems Laboratory
U.S. Environmental Protection Agency
P.O. Box 15027
Las Vegas, NV 89114
U. S. GOVERNMENT PRINTING OFFICE: 1984 — 759-015/7818
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Official Business
Penalty for Private Use $300
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