440-1-89-023
United States Environmental Protection Agency
Office of Water Regulations and Standards
Industrial Technology Division
Office of Water W/M«3 Jung-mao
Method 1624: Volatile Organic
Compounds by Isotope Dilution
GCMS
Method 1625: Semivolatile
Organic Compounds by Isotope
Dilution GCMS
-------
-------
Introduction
Methods 1624 and 1625 were developed by the Industrial
Technology Division (ITD) within the United States
Environmental Protection Agency's (USEPA) Office of Water
Regulations and Standards (OURS) to provide inproved precision
and accuracy of analysis of pollutants in aqueous and solid
matrices. The ITD is responsible for development and
promulgation of nationwide standards setting limits on
pollutant levels in industrial discharges.
Methods 1624 and 1625 are isotope dilution, gas
chromatography-mass spectrometry methods for analysis of the
volatile and semivolatile, organic "priority" pollutants, and
other organic pollutants amenable to gas chromtographymass
spectrometry. Isotope dilution is a technique which employs
stable, isotopically labeled analogs of the compounds of
interest as internal standards in the analysis.
Questions concerning the Methods or their application should
be addressed to:
U. A. Tel Hard
USEPA
Office of Water Regulations and Standards
401 M Street SW
Washington, DC 20460
202/382-7131
OR
USEPA OWRS
Sample Control Center
P.O. Box 1407
Alexandria, Virginia 22313
703/557-5040
Publication date: June 1989
-------
-------
Method 1624 Revision C June 1989
Volatile Organic Compounds by Isotope Dilution GCMS
1 SCOPE AND APPLICATION
1.1 This method is designed to meet the survey
requirements of the USEPA ITD. The method
is used to determine the volatile toxic
organic pollutants associated with the
Clean Water Act (as amended 1987); the
Resource Conservation and Recovery Act (as
amended 1986); the Comprehensive Environ-
mental Response, Compensation and
Liability Act (as amended 1986); and other
compounds amenable to purge and trap gas
chromatography-mass spectrometry (GCMS).
1.2 The chemical compounds listed in Tables 1
and 2 may be determined in waters, soils,
and municipal sludges by the method.
1.3 The detection limits of the method are
usually dependent on the level of
interferences rather than instrumental
limitations. The levels in Table 3 typify
the minimum quantities that can be
detected with no interferences present.
1.4 The GCMS portions of the method are for
use only by analysts experienced with GCMS
VOLATILE ORGANIC COMPOUNDS DETERMINED
Table 1
BY GCMS USING ISOTOPE
Pollutant
DILUTION AND INTERNAL STANDARD TECHNIQUES
Comoound
acetone
acrolein
acrylonitrile
benzene
bromodi ch I oromethane
bromoform
bromomethane
carbon tetrachloride
chlorobenzene
chloroethane
2-chloroethylvinyl ether
chloroform
chloromethane
di bromoch I oromethane
1,1 -di chloroethane
1,2-dichloroethane
1,1-dich loroethene
trans- 1 , 2-dichlorethene
1,2-dichloropropane
trans-1 ,3-dichloropropene
di ethyl ether
p-dioxane
ethylbenzene
methylene chloride
methyl ethyl ketone
1,1,2,2- tetrach loroethane
tetrach loroethene
toluene
1 , 1 , 1 -tri chloroethane
1 , 1 ,2-trichloroethane
trich loroethene
vinyl chloride
Storet
81552
34210
34215
34030
32101
32104
34413
32102
34301
34311
34576
32106
34418
32105
34496
32103
34501
34546
34541
34699
81576
81582
34371
34423
81595
34516
34475
34010
34506
34511
39180
39175
CAS Reaifttrv
67-64-1
107-02-8
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
56-23-5
108-90-7
75-00-3
110-75-8
67-66-3
74-87-3
124-48-1
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-02-6
60-29-7
123-91-1
100-41-4
75-09-2
78-93-3
79-34-5
127-18-4
108-88-3
71-55-6
79-00-5
79-01-6
75-01-4
516 V
002 V
003 V
004 V
048 V
047V
046 V
006 V
007 V
016 V
019 V
023 V
045 V
051 V
013 V
010 V
029 V
030 V
032 V
033 V
515 V
527 V
038 V
044 V
514 V
015 V
085 V
086 V
011 V
014 V
087V
088 V
uonce
001 V
002 V
003 V
012 V
005 V
020 V
006 V
007V
009 V
010 V
011 V
021 V
008 V
014 V
015 V
016 V
026 V
017 V
019 V
022 V
023 V
024 V
025 V
027V
028 V
029 V
031 V
d.
O
a*
4
d,
j
4
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d.
13C
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d*
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£
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13c,
13c
d,
i-aoeiea uomoour
666-52-4
33984-05-3
53807-26-4
1076^43-3
93952-10-4
72802-81-4
1111-88-2
32488-50-9
3114-55-4
19199-91-8
31717-44-9
1111-89-3
93951-99-6
56912-77-7
17070-07-0
22280-73-5
42366-47-2
93952-08-0
93951-86-1
2679-89-2
17647-74-4
25837-05-2
1665-00-5
53389-26-7
33685-54-0
32488-49-6
2037-26-5
2747-58-2
93952-09-1
93952-00-2
6745-35-3
iQ
616 V
202 V
203 V
204 V
248 V
247 V
246 V
206 V
207 V
216 V
223 V
245 V
251 V
213 V
210 V
229 V
230 V
232 V
233 V
615 V
627 V
238 V
244 V
614 V
215 V
285 V
286 V
211 V
214 V
287 V
288 V
-------
or under the close supervision of such
qualified persons. Laboratories unfamil-
iar with analysis of environmental samples
by GCMS should run the performance tests
in Reference 1 before beginning.
2 SUMMARY OF METHOD
2.1 The percent solids content of the sample
is determined. If the solids content is
known or determined to be less than one
percent, stable isotopically labeled
analogs of the compounds of interest are
added to a 5 mL simple and the sample is
purged with an inert gas at 20 - 25 "C in
a chamber designed for soil or water
samples. If the solids content is greater
than one percent, five mL of reagent water
and the labeled compounds are added to a 5
gram aliquot of sample and the mixture is
purged at 40 °C. Compounds that will not
purge at 20 - 25 "C or at 40 °C are purged
at 75 - 85 *C. (See Table 2). In the
purging process, the volatile compounds
are transferred from the aqueous phase
into the gaseous phase where they are
passed into a sorbent column and trapped.
After purging is completed, the trap is
backflushed and heated rapidly to desorb
the compounds into a gas chromatograph
(GC). The compounds are separated by the
GC and detected by a mass spectrometer
(MS) (References 2 and 3). The labeled
compounds serve to correct the variability
of the analytical technique.
2.2 Identification of a pollutant (qualitative
analysis) is performed in one of three
ways: (1) For compounds listed in Table 1
and other compounds for which authentic
standards are available, the GCMS system
is calibrated and the mass spectrum and
retention time for each standard are
stored in a user created library. A
compound is identified when its retention
time and mass spectrum agree with the
library retention time and spectrum. (2)
For compounds listed in Table 2 and other
compounds for which standards are not
available, a compound is identified when
the retention time and mass spectrum agree
with those specified in this method. (3)
For chromatographic peaks which are not
identified by (1) and (2) above, the
background corrected spectrum at the peak
maximum is compared with spectra in the
EPA/NIH Mass Spectral File (Reference 4).
Tentative identification is established
when the spectrum agrees (see Section 12).
2.3 Quantitative analysis is performed in one
of four ways by GCMS using extracted ion
current profile (EICP) areas: (1) For
compounds listed in Table 1 and other
compounds for which standards and labeled
analogs are available, the GCMS system is
Table 2
VOLATILE ORGANIC COMPOUNDS TO BE DETERMINED BY REVERSE SEARCH AND QUANTITATION USING KNOWN RETENTION TIMES,
RESPONSE FACTORS, REFERENCE COMPOUNDS, AND MASS SPECTRA
EGO
Ho. Con-pound
CAS Registry
532 allyl alcohol* 107-18-6
533 carbon disulfide 75-15-0
534 2-chloro-1,3-butadiene
(chloroprene) 126-99-8
535 chloroacetonitrile* 107-14-2
536 3-chloropropene 107-05-1
537 crotonaldehyde* 123-73-9
538 1,2-dibromoethane (EDB) 106-93-4
539 dibroraomethane 74-95-3
540 trans-1,4-
dichloro-2-butene 110-57-6
541 1,3-dichloropropane 142-28-9
542 cis-1,3-dichloropropene 10061-01-5
543 ethyl cyanide* 107-12-0
EGD
No.
Coffloound
CAS Registry
544 ethyl methacrylate 97-63-2
545 2-hexanone 591-78-6
546 iodomethane 74-88-4
547 isobutyl alcohol* 78-83-1
548 methacrylonitrile 126-98-7
549 methyl methacrylate 78-83-1
550 4-methyl-2-pentanone 108-10-1
551 1,1,1,2-tetrachloroethane 630-20-6
552 trichlorofluoromethane 75-69-4
553 1,2,3-trichloropropane 96-18-4
554 vinyl acetate 108-05-4
951 m-xylene 108-38-3
952 o- + p-xylene
* determined at a purge temperature of 75 - 85 "C
-------
calibrated and the compound concentration
is determined using an isotope dilution
technique. (2) For compounds listed in
Table 1 and for other compounds for which
authentic standards but no labeled
compounds are available, the GCMS system
is calibrated and the compound
concentration is determined using an
internal standard technique. (3) For
compounds listed in Table 2 and other
compounds for which standards are not
available, compound concentrations are
determined using known response factors.
(4) For compounds for which neither
standards nor known response factors are
available, compound concentration is
determined, using the sum of the EICP areas
relative to the sum of the EICP areas of
the nearest eluted internal standard.
2.4 The quality of the analysis is assured
through reproducible calibration and
testing of the purge and trap and GCMS
systems.
3 CONTAMINATION AND INTERFERENCES
3.1 Impurities in the purge gas, organic
compounds out-gassing from the plumbing
upstream of the trap, and solvent vapors
in the laboratory account for the majority
of contamination problems. The analytical
system is demonstrated to be free from
interferences under conditions of the
analysis by analyzing reagent water blanks
initially and with each sample batch
(samples analyzed on the same 8 hr shift),
as described in Section 8.5.
3.2 Samples can be contaminated by diffusion
of volatile organic compounds (particu-
larly methylene chloride) through the
bottle seal during shipment and storage.
A field blank prepared from reagent water
and carried through the sampling and
handling protocol may serve as a check on
such contamination.
3.3 Contamination by carry-over can occur when
high level and low level samples are
analyzed sequentially. To reduce carry-
over, the purging device (Figure 1 for
samples containing less than one percent
solids; Figure 2 for samples containing
one percent solids or greater) is cleaned
or replaced with a clean purging device
after each sample is analyzed. When an
unusually concentrated sample is
encountered, it is followed by analysis of
a reagent water blank to check for carry-
over. Purging devices are cleaned by
washing with soap solution, rinsing with
tap and distilled water, and drying in an
oven at 100-125 °C. The trap and other
parts of the system are also subject to
contamination; therefore, frequent bakeout
and purging of the entire system may be
required.
Table 3
GAS CHROHATOGRAPHY OF PURGEABLE ORGANIC COMPOUNDS
EGD
No.
0?
245
345
246
346
288
388
216
316
244
344
546
616
716
202
Retention time
Comoound
ch I oromethane-d,
chloromethane
bromomethane-dL
bromomethane
vinyl chloride-d.
vinyl chloride
ch I orpethane-d_
chloroethane
methylene chloride-d2
methylene chloride
iodomethane
acetone-dfi
acetone
acrolein-d.
Mean
(sec)
147
148
243
246
301
304
378
386
512
517
498
554
565
564
EGD
Ref
181
245
181
246
181
288
181
216
181
244
181
181
616
181
Relative (2)
0.141
0.922
0.233
0.898
0.286
0.946
0.373
0.999
0.582
0.999
0.68
0.628
0.984
0.641
- 0.270
- 1.210
- 0.423
- 1.195
- 0.501
- 1.023
- 0.620
- 1.060
- 0.813
- 1.017
- 0.889
- 1.019
- 0.903
Mini-
mum
Level
(3)
(ug/mL:
50
50
50
50
50
10
50
50
10
10
50
50
(5)
Method Detection
Limit (4)
low high
solids solids
> (ug/ko> fun/ken
207*
148*
190*
789*
566*
3561*
50
13
11
11
24
280*
322*
-------
Table 3 (continued)
GAS CHROMATOGRAPHY OF PURGEABLE ORGANIC COMPOUNDS
EGO
Ho.
(1)
302
203
303
533
552
543
229
329
536
532
181
213
313
615
715
230
330
614
714
223
323
535
210
310
539
548
547
211
311
627
727
206
306
554
248
348
534
537
232
332
542
287
387
541
204
304
251
351
214
314
Retention time
•crolein
acrylonftrile-dj
acrylonitrile
carbon disulf ide
tr ! ch lorof luoromethane
ethyl cyanide
1,1 -dichloroethene-d.
1,1-dichloroethene
3-chloropropene
allyl alcohol
broraochlorotnethane (I.S.)
1,1-dichloroethane-d-
1,1-dichloroethane
diethyl ether-d.-
diethyl ether
trans-1,2-dichloroethene-d2
trans-1,2-dichloroethene
methyl ethyl ketone-dj
methyl ethyl ketone
chloroform- C.
chloroform
chloroacetonitri le
1,2-dichloroethane-d^
1 , 2-di ch loroethane
dibroraomethane
raethacrylonitrile
isobutyl alcohol
1,1,1-trichloroethane-l3C2
1,1,1-trichloroethane
p-dioxane-dg
p-dioxane
carbon tetrachloride- C^
carbon tetrachloride
vinyl acetate
bromodichlorotnethane- C^ ,
bromodfchloromethan*
2-chloro-1,3-butadiene
crotonaldehyde
1 ,2-dichloropropane-d6
1,2-dichldropropane
cis-1 ,3-dichloropcopene
trichloroethene- Cg
trichloroethene
1 ,3-dichloropropane
benzene-dg
benzene _
chlorodibromomethane- C1
chlorodibromomethane
1,1,2-trichloroethane- C2
1 , 1 ,2-trichloroethane
Mean
(sec)
566
606
612
631
663
672
696
696
696
703
730
778
786
804
820
821
821
840
848
861
861
884
901
910
910
921
962
989
999
982
1001
1018
1018
1031
1045
1045
1084
1098
1123
1134
1138
1172
1187
1196
1200
1212
1222
1222
1224
1224
EGO
Ref
202
181
203
181
181
181
181
229
181
181
181
181
213
181
615
181
230
181
614
181
223
181
181
210
181
181
181
181
211
181
627
182
206
182
182
248
182
182
182
232
182
182
287
182
182
204
182
251
182
214
Relative (2)
0.984 -
0.735 -
0.985 -
0.86
0.91
0.92
0.903 -
0.999 -
0.95
0.96
1.000 -
1.031 -
0.999 -
1.067 -
1.010 -
1.056 -
0.996 -
0.646 -
0.992 -
1.092 -
0.961 -
1.21
1.187 -
0.973 -
1.25
1.26
1.32
1.293 -
0.989 -
1.262 -
1.008 -
0.754 -
0.938 -
0.79
0.766 -
0.978 -
0.83
0.84
0.830 -
0.984 -
0.87
0.897 -
0.991 -
0.92
0.888 -
1.002 -
0.915 -
0.989 -
0.922 -
0.975 -
1.018 (5)
0.926
1.030
0.976
1.011
.000
.119
.014
.254
.048
.228
.011
.202
.055
.322
.009
.416
.032
1.598
1.044
1.448 (5)
1.040 (5)
0.805
1.005
0.825
1.013
0.880
1.018 .
0.917
1.037
0.952
1.026
0.949
1.030
0.953
1.027
Mini-
mum
Level
(3)
-------
Table 3 (continued)
GAS CHROHATOGRAPHY OF PURGEABLE ORGANIC COMPOUNDS
Mini-
Method Detection
EGO
NO.
<1>
233
333
019
538
182
549
247
347
551
550
553
215
315
545
285
385
540
183
544
286
386
207
307
238
338
185
951
952
Retention time
Comjound
trans-1 ,3-dichloropropene-d,
trans- 1,3-dichloropropene
2-chloroethyl vinyl ether
1,2-dibromoethane
2-bramo-1-chloropropane (I.S.
methyl methacrylate
bromoform-13C1
bromoform
1,1,1 ,2-tetrachloroethane
4-methyl-2-pentanone
1 ,2,3-trichloropropane
1 , 1 ,2,2-tetrachloroethane-d-
1 , 1 ,2,2-tetrachloroethane'
2-hexanone
tetrach loroethene- 13C,
tetrach loroethene
trans-1, 4-dichloro-2-butene
1,4-dichlorobutane (int std)
ethyl methacrylate
toluene-d-
toluene
chlorobenzene-de
chlorobenzene
ethylbenzene-d.Q
ethylbenzene
bromof luorobenzene
m-xylene
o- + p-xylene
Mean
(sec)
1226
1226
1278
1279
1306
1379
1386
1386
1408
1435
1520
1525
1525
1525
1528
1528
1551
1555
1594
1603
1619
1679
1679
1802
1820
1985
2348
2446
EGD
Ref
182
233
182
182
182
182
182
247
182
183
183
183
215
183
183
285
183
183
183
183
286
183
207
183
238
183
183
183
Relative (2)
0.922 -
0.993 -
0.983 -
0.98
1.000 -
1.06
1.048 -
0.992 -
1.08
0.92
0.98
0.969 -
0.890 -
0.98
0.966 -
0.997 -
1.00
1.000 -
1.03
1.016 -
1.001 -
1.066 -
0.914 -
1.144 -
0.981 -
1.255 -
1.51
1.57
0.959
1.016
1.026
1.000
1.087
1.003
0.996
1.016
0.996
1.003
1.000
1.054
1.019
1.135
1.019
1.293
1.018
1.290
Level
(3)
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
low high
solids solids
(6)* (6)*
122 21
91 7
20 6
106 10
27 4
21 58*
28 4
*
(1) Reference numbers beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal standard
method; reference numbers beginning with 2 or 6 i.ndicate a labeled compound quantified by the internal
standard method; reference nunbers beginning with 3 or 7 indicate a pollutant quantified by isotope
dilution.
(2) The retention time limits in this column are based on data from four uastewater laboratories. The single
values for retention times in this column are based on data from one uasteuater laboratory.
(3) This is a minimum level at which the analytical system shall give recognizable mass spectra (background
corrected) and acceptable calibration points when calibrated using reagent water. The concentration in the
aqueous or solid phase is determined using the equations in section 13.
(4) Method detection limits determined in digested sludge (low solids) and in filter cake or compost (high
solids).
(5) Specification derived from related compound.
(6) An unknown interference in the particular sludge studied precluded measurement of the Method Detection
Limit (HDL) for this compound.
* Background levels of these compounds were present in the sludge resulting in higher than expected MDL's. The
MDL for these compounds is expectod to be approximately 20 ug/kg (100 - 200 for the gases and water soluble
compounds) for the low solids method and 5 • 10 ug/kg (25 - 50 for the gases and water soluble compounds) for
the high solids method, with no interferences present.
Column: 2.4 m (8 ft) x 2 am i.d. glans, packed with one percent SP-1000 coated on 60/80 Carbopak B.
Carrier gas: helium at 40 mL/min.
Temperature program: 3 min at 45 *C, 8 "C per min to 240 "C, hold at 240 "C for 15 minutes.
-------
3.4 Interferences resulting from samples will
vary considerably from source to source,
depending on the diversity of the site
being sampled.
4 SAFETY
4.1 The toxicity or cnrcinogenicity of each
compound or reagent used in this method
has not been precisely determined;
however, each chemical compound should be
treated as a potential health hazard.
Exposure to these compounds should be
reduced to the lowest possible level. The
laboratory is responsible .for maintaining
a current awareness file of OSHA
regulations regarding the safe handling of
the chemicals specified in this method. A
reference file of data handling sheets
should also be made available to all
personnel involved in these analyses.
Additional information on laboratory
safety can be found in References 5-7.
4.2 The following compounds covered by this
method have been tentatively classified as
known or suspected human or manna Iian car-
cinogens: benzene, carbon tetrachloride,
chloroform, and vinyl chloride. Primary
standards of these toxic compounds should
be prepared in a hood, and a.NIOSH/MESA
approved toxic gas respirator should be
worn when high concentrations are handled.
5 APPARATUS AND MATERIALS
5.1 Sample bottles for discrete sampling
5.1.1 Bottle--25 to 40 ml with screw cap (Pierce
13075, or equivalent). Detergent wash,
rinse with tap and distilled water, and
dry at >105 *C for one hr minimum before
use.
5.1.2 Septum—Teflon-facod silicone (Pierce
12722, or equivalent), cleaned as above
and baked at 100 - 200 °C for one hour
minimum.
5.2 Purge and trap device—consists of purging
device, trap, and desorber.
5.2.1 Purging devices for water and soil samples
5.2.1.1 Purging device for water samples—designed
to accept 5 mL samples with water column
at least 3 cm deep. The volume of the
gaseous head space between the water and
trap shall be less than 15 mL. The purge
gas shall be introduced less than 5 mm
from the base of the water column and
shall pass through the water as bubbles
with a diameter less than 3 mm. The
purging device shown in Figure 1 meets
these criteria.
OPTIONAL
FOAM TRAP
INLET 1M IN. O.O.
EXIT 1/4 IN. O.O.
10 MM GLASS FRIT
MEOWM POROSITY
SAMPLE INLET
2WAY SYRINGE VALVE
17 CM 20 OAUQE SYRINGE NEEDLE
6 MM O.O. RUBBER SEPTUM
INLET IM IN, 0.0.
_ 1/18 IN. 0.0.
.^STAINLESS STEEL
13X
MOLECULAR SIEVE
PURSE GAS FILTER
PURGE GAS
I FLOW CONTROL
FIGURE 1 Purging Device for Waters
5.2.1.2 Purging device for solid samples--designed
to accept 5 grams of solids plus 5 ml of
water. The volume of the gaseous head
space between the water and trap shall be
less than 25 mL. The purge gas shall be
introduced less than 5 mm from the base of
the sample and shall pass through the
water as; bubbles with a diameter less than
3 mm. The purging device shall be capable
of operating at ambient temperature (20 -
25 8C) and of being controlled at
temperatures of 40 ± 2 °C and 80 ± 5 °C
while the sample is being purged. The
purging device shown in Figure 2 meets
these criteria.
6
-------
PURGE INLET FITTING
SAMPLE OUTLET FITTING
3" X D MM 00. QLASS TUBINO
PACKING DETAIL
^ -5MM GLASS WOOL
7.7 CM SILICA GEL
CONSTRUCTION DETAIL
COMPRESSION
FITTING NUT
AND FERRULES
14 FT. 7niFOOT
RESISTANCE WIRE
WRAPPED SOLID
15CMTENAXOC
_*• 1CM3-.OV-1
-5 MM GLASS WOOL
TUBING 25 CM
0.105 IN. I.D.
0.125 IN. O.O.
STAINLESS STEEL
FIGURE2 Purging Device for Soils or Waters
5.2.2
5.2.2.1
Trap-25 to 30 cm x 2.5 mm i.d. mini
containing the following:
Methyl silicone packing—one ± 0.2 cm, 3
percent OV-1 on 60/80 mesh Chromosorb W,
or equivalent.
FIGURES Trap Construction and Packings
5.2.4 The purge and trap device may be a
separate unit, or coupled to a GC as shown
in Figures 4 and 5.
CARRIER GAS
• FLOW CONTROL
LIQUID INJECTION PORTS
COLUMN OVEN
5.2.2.2 Porous polymer--15 ± 1.0 cm. Tenax GC
(2,6-diphenylene oxide polymer), 60/80
mesh, chromatographic grade, or
equivalent.
OPTIONAL tPOBT COLUMN
SELECTION VALVE
5.2.2.3
5.2.3
Silica gel--8 ± 1.0 cm, Davison Chemical,
35/60 mesh, grade 15, or equivalent. The
trap shown in Figure 3 meets these
specifications.
Desorber—shall heat the trap to 175 t 5
°C in 45 seconds or. less. . The polymer
section of the trap shall not exceed a
temperature of 180 °c and the remaining
sections shall not exceed 220 "C during
desorb, and no portion of the trap shell
exceed 225 "C during bakeout. The
desorber shown in Figure 3 meets these
specifications.
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
PURGING
DEVICE
NOTE
ALL LINES BETWEEN TRAP
AND GC SHOULD BE HEATED
10 HOC
FIGURE 4 Schematic of Purge and Trap
Device-Purge Mode
-------
CAIWCKOAI
UOUO INJECTION PORTS
COLUMN OVEN
y— CONFIRMATORY COLUMN
ALL LINES BETWEEN TRAP
AND OC SHOULD B€ HEATED
TO WC.
FIGURES Schematic of Purge and Trap
Devlce-Desorb Mode
5.3
5.3.1
5.4
5.5
Gas chrom«tograph--shall be linearly
temperature programmable with initial and
final holds, shall contain a glass jet
separator as the MS interface, and shall
produce results which meet the calibration
(Section 7), quality assurance (Section
8), and performance tests (Section 11) of
this method.
Colum—2.8 ± 0.4 HJ x 2 ± 0.5 nw i.d.
glass, packed with one percent SP-1000 on
Carbopak B, 60/80 mesh, or equivalent.
Mass spectroweter—70 eV electron impact
fonization; shall repetitively scan from
20 to 250 arou every 2-3 seconds, and
produce a unit resolution (valleys between
ra/z 174-176 less than 10 percent of the
height of the m/z 175 peak), background
corrected mass spectrum from 50 ng 4-
bromofluorobenzene (BFB) injected into the
GC. The BFB spectrum shall meet the mass-
intensity criteria in Table 4. All
portions of the GC column, transfer lines,
and separator which connect the GC column
to the ion source shall remain at or above
the column temperature during analysis to
preclude condensation of less volatile
compounds.
Data system—shall collect and record MS
data, store mass-intensity data in
spectral libraries, process GCHS data and
generate reports, and shall calculate and
record response factors.
5.5.1
5.5.2
Table 4
BFB MASS-INTENSITY SPECIFICATIONS
m/z Intensity Required
50 15 to 40 percent of m/z 95
75 30 to 60 percent of m/z 95
95 base peak, 100 percent
96 5 to 9 percent of m/z 95
173 less than 2 percent of m/z 174
174 greater than 50 percent of m/z 95
175 5 to 9 percent of m/z 174
176 95 to 101 percent of m/z 174
177 5 to 9 percent of m/z 176
Data acquisition—mass spectra shall be
collected continuously throughout the
analysis and stored on a mass storage
device.
Mass spectral libraries—user created
libraries containing mass spectra obtained
from analysis of authentic standards shall
be employed to reverse search GCMS runs
for the compounds of interest (Section
7.2).
Data processing--the data system shall be
used to search, locate, identify, and
quantify the compounds of .interest in each
GCMS analysis. Software routines shall be
employed to compute retention times and
EICP areas. Displays of spectra, mass
chromatograms, and library comparisons are
required to verify results.
5.5.4 Response factors and multipoint calibra-
tions—the data system shall be used to
record and maintain lists of response
factors (response ratios for isotope dilu-
tion) and generate multi-point calibration
curves (Section 7). Computations of rela-
tive standard deviation (coefficient of
variation) are useful for testing calibra-
tion linearity. Statistics on initial and
on-going performance shall be maintained
(Sections 8 and 11).
5.5.3
5.6 Syringes—5 mL
Luer-lok tips.
glass hypodermic, with
5.7 Micro syringes--10, 25, and 100 uL.
8
-------
5.8
5.9
5.10
5.11
5.11.1
5.11.2
5.12
5.12.1
5.12.2
5.12.3
6
6.1
6.1.1
6.1.2
6.1.3
6.2
6.3
6.4
Syringe valves-2-way, with Luer ends
(Teflon or Kel-F).
Syringe-5 mL, gas-tfght, with shut-off
valve.
Bottles-15 raL, screw-cap with Teflon
liner.
Balances
Analytical, capable of weighing 0.1 mg.
Top loading, capable of weighing 10 ing.
Equipment for determining percent moisture
Oven. capable of being temperature
controlled at 110 ± 5 °C.
Dessicator.
Beakers--50 - 100 mL.
REAGENTS AND STANDARDS
Reagent water-water in which the
compounds of interest and interfering
compounds are not detected by this method
(Section 11.7). it may be generated by
any of the following methods:
Activated carbon—pass tap water through a
carbon bed (Calgon Filtrasorb-300, or
equivalent).
Water purifier-pass tap water through a
purifier (Millipore Super o. or
equivalent).
Boil and purge—heat tap water to 90-100
°C and bubble contaminant free inert gas
through it for approximately one hour.
While still hot, transfer the water to
screw-cap bottles and seal with a Teflon-
lined cap.
Sodium thiosulfate—ACS granular.
Hethanol—pesticide quality or equivalent.
Standard solutions—purchased as solutions
or mixtures with certification to their
purity, concentration, and authenticity,
or prepared from materials of known purity
and composition. If compound purity is 96
percent or greater, the weight may be used
6.5
6.5.1
without correction to calculate the
concentration of the standard.
Preparation of stock solutions--prepare in
methanol using liquid or gaseous standards
per the steps below. Observe the safety
precautions given in Section 4.
Place approximately 9.8 mL of methanol in
a 10 mL ground glass stoppered volumetric
flask. Allow the flask to stand unstop-
pered for approximately 10 minutes or un-
til all methanol wetted surfaces have
dried.
In each case, weigh the flask, inroediately
add the compound, then immediately reweigh
to prevent evaporation losses from
affecting the measurement.
Liquids-using a 100 uL syringe, permit 2
drops of liquid to fall into the methanol
without contacting the neck of the flask.
Alternatively, inject a known volume of
the compound into the methanol in the
flask using a micro-syringe.
6.5.1.2 Gases (chloromethane. bromomethane.
chloroethane, vinyl chloride)--fill a
valved 5 mL gas-tight syringe with the
compound.
Lower the needle to approximately 5 mm
above the methanol meniscus. Slowly
introduce the compound above the surface
of the meniscus. The gas will dissolve
rapidly in the methanol.
6.5.1.1
6.5.2
6.5.3
6.5.4
Fill the flask to volume, 'stopper, then
mix by inverting several times. Calculate
the concentration in mg/mL (ug/uL) from
the weight gain (or density if a known
volume was injected).
Transfer the stock solution to a Teflon
sealed screw-cap bottle.
Store, with minimal headspace, in the dark
at -10 to -20 "C.
Prepare fresh standards weekly for the
gases and 2-chloroethylvinyl ether. All
other standards are replaced after one,
month, or sooner if comparison with check
standards indicate a change in concentra-
tion. Quality control check standards
-------
that can be used to determine the accuracy
of calibration standards are available
from the US Environmental Protection
Agency, Environmental Monitoring and Sup-
port Laboratory, Cincinnati, Ohio.
6.6 Labeled compound spiking solution—fro*
stock standard solutions prepared ««
above, or from mixtures, prepare the spik-
ing solution to contain a concentration
such that a 5-10 uL spike into each 5 nL
sample, blank, or aqueous standard ana-
lyzed will result in a concentration of 20
ug/L of each labeled compound. Tor the
gases and for the water soluble compounds
(acrolein, acrylonitrile, acetone, diethyl
ether, p-dioxane, and MEK), a
concentration of 100 ug/L may be used.
Include the internal standards (Section
7.5) in this solution so that a
concentration of 20 ug/L in each sample,
blank, or aqueous standard will be
produced.
6.7 Secondary standards—using stock solu-
tions, prepare a secondary standard in
methanol to contain each pollutant at a
concentration of 500 ug/raL. For the gases
and water soluble compounds (Section 6.6),
a concentration of 2.5 mg/raL nay be used.
6.7.1 ' Aqueous calibration standards-using a 25
uL syringe, add 20 uL of the secondary
standard (Section 6.7) to 50, 100, 200,
500, and 1000 mL of reagent water to
produce concentrations of 200, 100, 50,
20, and 10 ug/L, respectively. If the
higher concentration standard for the
gases and water soluble compounds was
chosen (Section 6.6), these compounds will
be at concentrations of 1000, 500, 250,
100, and 50 ug/L in the aqueous
calibration standards.
6.7.2 Aqueous performance standard—an aqueous
standard containing all pollutants,
internal standards, labeled compounds, and
BFB is prepared daily, and analyzed each
shift to demonstrate performance (Section
11). This standard shall contain either
20 or 100 ug/L of the labeled and
pollutant gases and water soluble
compounds, 10 ug/L BFB, and 20 ug/L of all
other pollutants, labeled compounds, and
internal standards. It may be the nominal
20 ug/L aqueous calibration standard
(Section 6.7.1).
6.7.3 A methanolic standard containing all
pollutants and internal standards is
prepared to demonstrate recovery of these
compounds, when syringe injection and purge
and trap analyses are compared.
This standard shall contain either 100
ug/mL or 500 ug/mL of the gases and water
soluble compounds, and 100 ug/mL of the
remaining pollutants and internal
standardn (consistent with the amounts in
the aqueous performance standard in
6.7.2).
6.7.4 Other standards which may be needed are
those for test of BFB performance (Section
7.1) and for collection of mass spectra
for storage in spectral libraries (Section
7.2).
7 CALIBRATION
Calibration of the GCMS system is
performed by purging the compounds of
interest: and their labeled analogs from
reagent water at the temperature to be
used for analysis of samples.
7.1 Assemble the gas chromatographic apparatus
and establish operating conditions given
in Table 3. By injecting standards into
the GC, demonstrate that the analytical
system meets the minimum levels in Table 3
for the compounds for which calibration is
to be performed, and the mass-intensity
criteria in Table 4 for 50 ng BFB.
7.2 Mass spectral libraries—detection and
identification of the compounds of
interest are dependent upon the spectra
stored in user created libraries.
7.2.1 For the compounds in Table 1 and other
compounds for which the GCMS is to be
calibrated, obtain a mass spectrum of each
pollutant and labeled compound and each
internal standard by analyzing an
authentic standard either singly or as
part of a mixture in which there is no
interference between closely eluted
components. Examine the spectrum to
determine that only a single compound is
present. Fragments not attributable to
the compound under study indicate the
presence of an interfering compound.
Adjust the analytical conditions and scan
10
-------
7.2.2
7.2.3
7.2.4
rate (for this test only) to produce «n
undi stor ted spectrum at the GC peak
maximum. An undi stor ted spectrum will
usually be obtained if five complete
spectra are collected across the upper
half of the GC peak. Software algorithm
designed to "enhance" the spectrum my
eliminate distortion, but may also
eliminate authentic m/z's or introduce
other distortion.
The authentic reference spectrum is
obtained under BFB tuning conditions
(Section 7.1 and Table 4) to normalize it
to spectra from other instruments.
The spectrum is edited by saving the 5
most intense mass spectral peaks and all
other mass spectral peaks greater than 10
percent of the base peak. The spectrum
may be further edited to remove common
interfering masses. If 5 mass spectral
peaks cannot be obtained under the scan
conditions given in Section 5.4, the mass
spectrometer may be scanned to an M/Z
lower than 20 to gain additional spectral
information. The spectrum obtained is
stored for reverse search and for compound
confirmation.
For the compounds in Table 2 and other
compounds for which the mass spectra.
quantisation m/z's, and retention times
are known but the instrument is not to be
calibrated, add the retention time and
reference compound (Table 3); the response
factor and the quantitation m/z (Table 5);
and spectrum (Appendix A) to the reverse
search library. Edit the spectrum per
Section 7.2.3, if necessary.
7.3 Assemble the purge and trap device. Pack
the trap as shown in Figure 3 and
condition overnight at 170 - 180 ec by
backf lush ing with an inert gas at a flow
rate of 20 - 30 mL/min. Condition traps
daily for a minimum of 10 minutes prior to
use.
7.3.1 Analyze the aqueous performance standard
(Section 6.7.2) according to the purge and
trap procedure in Section 10. Compute the
area at the primary m/z (Table 5) for each
compound. Compare these areas to those
obtained by injecting one uL of the
methanolic standard (Section 6.7.3) to
determine compound recovery. The recovery
shall be greater than 20 percent for the
water soluble compounds (Section 6.6), and
60 - 110 percent for all other compounds.
This recovery is demonstrated initially
for each purge and trap GCHS system. The
test is repeated only if the purge and
Table 5
VOLATILE ORGANIC COMPOUND CHARACTERISTIC M/Z'S
Compound
acetone
acrolein
acrylonitrile
allyl alcohol
benzene
2-bromo-1-chloropropane (4)
bromochloromethane (4)
bromodich loromethane
bromoform
bromomethane
carbon disulfide
carbon tetrachloride
2-chloro-1 ,3-butadiene
chloroacetonitri le
chlorobenzene
chloroethane
2-chloroethylvinyl ether
Labeled
Analog
d.
dj
d.
6
13C
13C
13C
d.
Primary
m/z (1)
58/64
56/60
53/56
57
78/84
77
128
83/86
173/176
96/99
76
47/48
53
75
112/117
64/71
106/113
Reference
compound
(2)
181
181
182
181
Response factor at
purge temp, of:
20 °C 80 °c
(3)
1.93
0.29
(3)
0.20
2.02
0.50
1.12
11
-------
Table S (continued)
VOLATILE ORGANIC COMPOUND CHARACTERISTIC H/Z'!i
chloroform
chloromethane
3-chloropropene
crotonaldehyde
dibromoch loromethane
1 ,2-dibromoethane
dibromomethane
1,4-dichlorobutane (4)
trans-1,4-dichloro-2-butene
1,1-dtchloroethane
1,2-dichloroethane
1,1-dichloroethene
trans-1 ,2-dichlorethene
1,2-dichloropropene
1,3-dichloropropane
cis-1 ,3-dichloropropene
tram-1 ,3-dichloropropene
diethyl ether
p-dioxane
ethyl cyanide
ethyl methacrylate
ethylbenzene
2-hexanone
iodocnethane
isobutyl alcohol
methylene chloride
methyl ethyl ketone
methyl raethacrylate
4-methyl-2-pentanone
methacrylonitrile
1 , 1 ,1 ,2-tetrachloroethane
1 ,1 ,2,2-tetrachloroethane
tetrachloroethene
toluene
1,1,1-trichloroethane
1 ,1 ,2-trichloroethane
trichloroethene
trichlorofluoromethane
1 ,2,3-trichloropropane
vinyl acetate
vinyl chloride
m-xylene
o- + p-xylene
Labeled Primary
Analog m/z (1)
13C 85/86
d, 50/53
76
13 TO
13C 129/130
107
93
55
75
d, 63/66
df 62/67
d! 61/65
df 61/65
dT 63/67
76
75
d, 75/79
d* 74/84
dT 88/96
54
69
d1fl 106/116
10 58
142
74
d, 84/88
df 72/80
^ 69
58
67
131
13*2 83/84
"cf 164/172
dl 92/100
d, 97/102
"cl 83/84
13C, 95/136
Z 101
75
86
d. 62/65
^ 106
106
Reference
compound
(2)
181
182
182
181
183
182
182
181
183
183
181
181
182
183
181
182
181
183
182
183
183
Response factor at
purge temp, of
20 °C 80 °C
0.43
(3)
0.86
1.35
0.093
0.89
0.29
(3)
0.69
0.076
4.55
(3)
0.23
0.15
0.25
0.20
2.31
0.89
0.054
1.69
3.33
0.63
0.090
0.68
1.91
0.14
0.88
0.41
1.26
0.52
0.33
2.55
0.22
0.79
0.29
0.79
0.25
2.19
0.72
0.19
~
(1) native/labeled
(2) 181 - bromochloroiiiethane 182 * 2-bromo-1-chlorepropane 183 * 1,4-dichlorobutane
(3) not detected at a purse temperature of 20 "C
(4) internal standard
NOTE: lecaute the competition and purity of commercially-supplied isotopically labeled standards may vary, the
primary m/r of the labeled analog* given in this table should be used as guidance. The appropriate m/z of the
labeled analogs should be determined prior to use for sample analysis. Deviations from the m/z's listed here
must be documented by the laboratory and submitted with the data.
12
-------
trap or GCHS systems are modified in any
way that might result in a change in
recovery.
7.3.2 Demonstrate . that 100 ng toluene (or
toluene-dg) produces an area at m/z 91 (or
99) approximately one-tenth that required
to exceed the linear range of the system.
The exact value must be determined by
experience for each instrument. It is
used to match the calibration range of the
instrument to the analytical range and
detection limits required.
7.4 Calibration by isotope dilution—the iso-
tope dilution approach is used for the
purgeable organic compounds when appropri-
ate labeled compounds are available and
when interferences do not preclude the
analysis. If labeled compounds are not
available, or interferences are present,
the internal standard method (Section 7.5)
is used. A calibration curve encompassing
the concentration range of interest is
prepared for each compound determined.'
The relative response (RR) vs concentra-
tion (ug/L) is plotted or computed using a
linear regression. An example of a
calibration curve for toluene using
toluene-d8 is given in Figure 6.
10-
1.0-
UJ
IT
0.1-
2 10 20 50 100 200
CONCENTRATION (ug/L)
FIGURES Relative Response Calibration Curve for
Toluene. The Dotted Lines Enclose a +/- 10 Percent
Error Window
7.4.1
Also shown are the ± 10 percent error
limits (dotted lines). Relative response
is determined according to the procedures
described below. A minimum of five data
points are required for calibration
(Section 7.4.4).
The relative response (RR) of pollutant to
labeled compound is determined from iso-
tope ratio values calculated from acquired
data. Three isotope ratios are used in
this process:
RX = the isotope ratio measured in the
pure pollutant (Figure 7A).
R * the isotope ratio of pure labeled
compound (Figure 7B).
Rm = the 1"sot°Pe ratl"° measured in the an-
alytical mixture of the pollutant and la-
beled compounds (Figure 7C).
(A)
AREA=168920
• M/Z 100
• M/Z 92
(B)
AREA =60960
•M/Z 100
• M/Z 92
(C)
M/Z 92 _ 96868
M/Z 100" 82508
•M/Z 100
• M/Z 92
FIGURE? Extracted Ion Current Profiles for (A)
Toluene, (B) Toluene-ds, and (C) a Mixture of
Toluene and Toluene-ds
The correct way to calculate RR is:
If Rm is not between 2R and 0.5R , the
method does not apply and the sample is
13
-------
analyzed by the internal standard method
(Section 7.5).
7.4.2 In moat caatt, the retention tinea of the
pollutant and labeled compound are the
same, and isotope ratios (R's) can be cal-
culated fro« the EICP areas, where:
R • (area at ii./z)
(area at
If either of the areaa is zero, it is as-
signed a value of one in the calculations;
that is, if:
area of mjz * 50721, and
7.4.3
area of
« 0, then
R » 50721 « 50720
1
The data fro* these tnalyses are reported
to three significant figures (see Section
13.6). In order eo prevent rounding
errors fro* affecting the values to be
reported, all calculations performed prior
to the final- determination of
concentrations should be carried out using
at least four significant figures.
Therefore, the calculation of R above is
rounded to four significant figures.
The m/z's are always selected such that RX
When there is a difference in re-
^
tention times CRT) between the pollutant
and labeled compounds, special precautions
are required to determine the isotope ra-
tios.
RX, R , and Rm are defined as follows:
z (at RTM.
[ares m^z (at RT2>J
R- » t«reiJ«t/» (»t_
[area rn^z (at RTJH
An example of the above calculations can
be taken from the data plotted in Figure 7
for toluene and toluene-rig. For these
data:
Rv - 168920 » 168900
R * 1 » 0.00001640
y 60960
R * 96868 » 1.174
82508
The RR for the above data is then calcu-
lated using the equation given in Section
7.4.1. For the example, rounded to four
significant figures, RR » 1.174. Mot all
labeled compounds elute before their
pollutant analogs.
7.4.4 To calibrate the analytical system by
isotope dilution, analyze a 5 ml aliquot
of each of the aqueous calibration
standards (Section 6.7.1) spiked with an
appropriate constant amount of the labeled
compound spiking solution (Section 6.6),
using the purge and trap procedure in
Section 1C). Compute the RR at each
concentration.
7.4.5 Unearity-if the ratio of relative
response to concentration for any compound
is constant (less than 20 percent
coefficient of variation) over the 5 point
calibration range, an averaged relative
response/concentration ratio may be used
for that compound; otherwise, the complete
calibration curve for that compound shall
be used over the 5 point calibration
range.
7.5 Calibration by internal standard--used
when criteria for isotope dilution
(Section 7.4) cannot be met. The method
is applied to pollutants having no labeled
analog and to the labeled compounds.
The internal standards used for volatiles
analyses are bromochloromethane, 2-bromo-
1-chloropropane, and 1,4-dichlorobutane.
Concentrations of the labeled compounds
and pollutants without labeled analogs are
computed relative to the nearest eluting
internal standard, as shown in Tables 3
and 5.
7.5.1 Response factors—calibration requires the
determination of response factors
-------
AS is the EICP area at the characteristic
m/z for. the compound in the daily stan-
dard.
Ajs is the EICP area at the characteristic
m/z for the internal standard.
C.g is the concentration (ug/L) of the in-
ternal standard.
C8 is the concentration of the pollutant
in the daily standard.
7.5.2 The response factor is determined at 10,
20, 50, 100, and 200 ug/L for the
pollutants (optionally at five times these
concentrations for gases and water soluble
pollutants—see Section 6.7), in a way
analogous to that for calibration by
isotope dilution (Section 7.4.4). The RF
is plotted against concentration for each
compound in the standard (C } to produce a
calibration curve.
,7.5.3 Linearity—if the response factor (RF) for
any compound is constant (less than 35
percent coefficient of variation) over the
5 point calibration range, an averaged
response factor may be used for that
compound; otherwise, the complete
calibration curve for that compound shall
be used over the 5 point range-.
7.6 Combined calibration—by adding the
isotopically labeled compounds and
internal standards (Section 6.6) to the
aqueous calibration standards (Section
6.7.1), a single set of analyses can be
used to produce calibration curves for the
isotope dilution and internal standard
methods. These curves are verified each
shift (Section 11.5) by purging the
aqueous performance standard (Section
6.7.2).
Recalibration is required only if
calibration and on-going performance
(Section 11.5) criteria cannot be met.
7.7 Elevated purge temperature calibration-
samples containing greater than one
percent solids are analyzed at a
temperature of 40 ± 2 "C (Section 10).
For these samples, the analytical system
may be calibrated using a purge
temperature of 40 t 2 °C in order to more
closely approximate the behavior of the
compounds of _ interest in high solids
samples.
8 QUALITY ASSURANCE/QUALITY CONTROL
8.1 Each laboratory that uses this method is
required to operate a formal quality
assurance program (Reference 8). The
minimum requirements of this program
consist of an initial demonstration of
laboratory capability, analysis of samples
spiked with labeled compounds to evaluate
and document data quality, and analysis of
standards and blanks as tests of continued
performance. Laboratory performance is
compared to established performance
criteria to determine if the results of
analyses meet the performance
characteristics of the method.
8.1.1 The analyst shall make an initial
demonstration of the ability to generate
acceptable accuracy and precision with
this method. This ability is established
as described in Section 8.2.
8.1.2 The analyst is permitted to modify this
method to improve separations or lower the
costs of measurements, provided all
performance specifications are met. Each
time a modification is made to the method,
the analyst is required to repeat the
procedure in Section 8.2 to demonstrate
method performance.
8.1.3 Analyses of blanks are required to
demonstrate freedom from contamination and
that the compounds of interest and
interfering compounds have not been
carried over from a previous analysis
(Section 3). The procedures and criteria
for analysis of a blank are described in
Sections 8.5.
8.1.4 The laboratory shall spike all samples
with labeled compounds to monitor method
performance. This test is described in
Section 8.3. When results of these spikes
indicate atypical method performance for
samples, the samples are diluted to bring
method performance within acceptable
limits (Section 14.2).
8.1.5 The laboratory shall, on an ongoing basis,
demonstrate through the analysis of the
aqueous performance standard (Section
6.7.2) that the analysis system is in
control. This procedure is described in
Sections 11.1 and 11.5.
15
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8.1.6 The laboratory shall maintain records to
define the quality of data that is
generated. Development of accuracy
statements is described in Sections 8.4
and 11.5.2.
8.2 Initial precision and accuracy—to
establish the ability to generate
acceptable precision and accuracy, the
analyst shall perform the following
operations for compounds to be calibrated:
8.2.1 Analyze two sets of four 5-mL aliquots (8
aliquots total) of the aqueous performance
standard (Section 6.7.2) according to the
method beginning in Section 10.
8.2.2 Using results of the first set of four
analyses in Section 8.2.1, compute the
average recovery (X) in ug/L and the
standard deviation of the recovery (s) in
ug/L for each compound, by isotope
dilution for pollutants with a labeled
analog, and by internal standard for
labeled compounds and pollutants with no
labeled analog.
8.2.3 For each compound, compare s and X with
the corresponding limits for initial
precision and accuracy found in Table 6.
If s and X for all compounds meet the
acceptance criteria, system performance is
acceptable and analysis of blanks and
samples may begin. If, however, any
individual s exceeds the precision limit
or any individual X falls outside the
range for accuracy, system performance is
unacceptable for that compound.
NOTE: The large number of compounds in
Table 6 present a substantial probability
that one or more will fail one of the
acceptance criteria when all compounds are
analyzed. To determine if the analytical
system is out of control, or if the
failure can be attributed to probability,
proceed as follows:
8.2.4 Using the results of the second set of
four analyses, compute s and X for only
those compounds which failed the test of
the first set of four analyses (Section
8.2.3). If these compounds now pass,
system performance is acceptable for all
compounds and analysis of blanks and
samples may begin. If, however, any of
the same compounds fail again, the
analysis system is not performing properly
for the compound of the
labeled compounds using the internal
standard method (Section 7.5).
8.3.3 Compare the percent recovery for each
compound with the corresponding labeled
compound recovery limit in Table 6. If
the recovery of any compound falls outside
its warning limit, method performance is
unacceptable for that compound in that
sample.
Therefore, the sample matrix is complex
and the sample is to be diluted and
reanalyzed, per Section 14.2.
8.4 As part of the QA program for the
laboratory, method accuracy for wastewater
samples shall be assessed and records
shall be maintained. After the analysis
of five wastewater samples for which the
labeled compounds pass the tests in
Section 8.3.3, compute the average percent
recovery (P) and the standard deviation of
the percent recovery (s ) for the labeled
compounds only. Express the accuracy
assessment as a percent recovery interval
from P •• 2s to P +' 2s . For example, if
P = 90% and s = °0%, the accuracy
interval is expressed as 70 - 110%.
Update the accuracy assessment for each
compound on a regular basis (e.g. after
each 5 - 10 new accuracy measurements).
8.5 Blanks--reagent water blanks are analyzed
to demonstrate freedom from carry-over
(Section 3) and contamination.
8.5.1 The level at which the purge and trap
system will carry greater than 5 ug/L of a
pollutant of interest (Tables 1 and 2)
into a succeeding blank shall be
determined by analyzing successively
larger concentrations of these compounds.
16
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Table 6
ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS
Acceotanee
EGO
No.
(1)
516
002
003
004
048
047
046
006
007
016
019
023
045
051
013
010
029
030
032
033
515
527
038
044
514
015
085
086
011
014
087
088
Compound
acetone*
acrolein*
acrylonitrf le*
benzene
branodichloromethane
bromoform
bromomethane
carbon tetrachloride
chlorobenzene
chloroethane
2-chloroethylvinyl ether
chloroform
chloromethane
dibromochloromethane
1,1-di chloroethane
1 ,2-dichloroethane
1 , 1-dichloroethene
trans-1, 2-dichloroethene
1 , 2-di ch I oropropane
trans-1 ,3-dichloropropene
diethyl ether*
p-dioxane*
ethylbenzene
methylene chloride
methyl ethyl ketone*
1 ,1 ,2,2-tetrachloroethane
tetrachloroethene
toluene
1,1,1-tn" chloroethane
1,1,2-trichloroethane
trichloroethene
vinyl chloride
criteria
Labeled and native
compound initial
precision and accuracy
(Sect. 8.2.3)
9 (ua/L
51.0
72.0
16.0
9.0
8.2
7.0
25.0
6.9
8.2
15.0
36.0
7.9
26.0
7.9
6.7
7.7
12.0
7.4
19.0
15.0
44.0
7.2
9.6
9.7
57.0
9.6
6.6
6.3
5.9
7.1
8.9
28.0
) X Reference numbers beginning with 0. 1. or 5 indicate a pollutant quantified by the internal standard
method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the
jnternal^standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by
17
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When a sample contains this concentration
or more, • blank shall be analyzed
ifnaediately following this sample to
demonstrate no carry-over at the 5 ug/L
level.
.5.2 With each sample lot (samples analyzed on
the same 8 hr shift), a blank shall ba
analyzed immediately after analysis of the
aqueous performance standard (Section
11.1) to demonstrate freedom from
contamination. If any of the compounds of
interest (Tables 1 and 2) or any
potentially interfering compound is found
in a blank at greater than 10 ug/L
(assuming a response factor of 1 relative
to the nearest eluted internal standard
for compounds not listed in Tables 1 and
2), analysis of samples is halted until
the source of contamination is eliminated
and a blank shows no evidence of
contamination at this level. *
8.6 The specifications contained in this
method can be met if the apparatus used is
calibrated properly, then maintained in a
calibrated state. The standards used for
calibration (Section 7), calibration
verification (Section 11.5) and for
initial (Section 8.2) and on-going
(Section 11.5) precision and accuracy
should be identical, so that .the most
precise results will be obtained. The
GCHS instrument in particular will provide
the most reproducible results if dedicated
to the settings and conditions required
for the analyses of volatiles by this
method.
8.7 Depending on specific program require-
ments, field replicates may be collected
to determine the precision of the sampling
technique, and spiked samples may be re-
quired to determine the accuracy of the
analysis when the internal method is used.
9 SAMPLE COLLECTION, PRESERVATION, AHD
HANDLING
9.1 Grab samples are collected in glass
containers having a total volume greater
than 20 mL. For aqueous samples which
pour freely, fill sample bottles so that
no air bubbles pass through the sample as
the bottle is filled and seal each bottle
so that no air bubbles are entrapped.
Maintain the hermetic seal on the sample
bottle until time of analysis.
9.2 Samples are maintained at 0 - 4 °C from
the time of collection until analysis. If
an aqueous sample contains residual
chlorine, add sodium thiosulfate
preservative (10 mg/40 mL) to the empty
sample battles just prior to shipment to
the sample site. EPA Methods 330.4 and
330.5 may be used for measurement of
residual chlorine (Reference 9). If
preservative has been added, shake the
bottle vigorously for one minute
immediately after filling.
9.3 For aqueous samples, experimental evidence
indicates that some aromatic compounds,
notably benzene, toluene, and ethyl
benzene are susceptible to rapid
biological degradation under certain
environmental conditions. Refrigeration
alone may not be adequate to preserve
these compounds in wastewaters for more
than- seven days.
For this reason, a separate sample should
be collected, acidified, and analyzed when
these aromatics are to be determined.
Collect about 500 mL of sample in a clean
container. Adjust the pH of the sample to
about 2 by adding HCl (1+1) while
stirring., Check pH with narrow range (1.4
to 2.8) pH paper. Fill a sample container
as described in Section 9.1. If residual
chlorine is present, add sodium
thiosulfate to a separate sample container
and fill as in Section 9.1.
9.4 All samples shall be analyzed within 14
days of collection.
10 PURGE, TRAP, AND GCMS ANALYSIS
Samples containing less than one percent
solids tire analyzed directly as aqueous
samples (Section 10.4). Samples con-
taining one percent solids or greater are
analyzed as solid samples utilizing one of
two methods, depending on the levels of
pollutants in the sample. Samples
containing one percent solids or greater,
and low to moderate levels of pollutants
are analyzed by purging a known weight of
sample added to 5 mL of reagent water
(Section 10.5). Samples containing one
percent solids or greater, and high levels
of pollutants are extracted with methanol,
and an aliquot of the methanol extract is
added to reagent water and purged (Section
10.6).
18
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10.1 Determination of percent solids
10.1.1 Weigh 5 - 10 g of sample into a tared
beaker.
10.1.2 Dry overnight <12 hours minimum) at 110 *
5 °C, and cool in a dessicator.
10.1.3 Determine percent solids as follows:
% solids = weight of sample dry x 100
weight of sample wet
10.2 Remove standards and samples from cold
. storage and bring to 20 - 25 °C.
10.3 Adjust the purge gas flow rate to 40 t 4
• . mL/min.
10.4 Samples containing less than one percent
solids
10.4.1 Mix the sample by shaking vigorously.
Remove the plunger from a 5 at. syringe and
attach a closed syringe valve. Open the
sample bottle and carefully pour the
sample into the syringe barrel until it
overflows. Replace the plunger and
compress the sample. Open the syringe
valve and vent any residual air while
adjusting the sample volume to 5.0 t 0.1
ml. Because this process of taking an
aliquot destroys the validity of the
sample for future analysis, fill a second
syringe at this time to protect against
possible loss of data.
10.4.2 Add an appropriate amount of the labeled
compound spiking solution (Section 6.6)
through the valve bore, then close the
valve. '
10.4.3 Attach the syringe valve assembly to the
syringe valve on the purging device. Open
both syringe valves and inject the sample
into the purging chamber. Purge the
sample per Section 10.7.
10.5 Samples containing one percent solids or
greater, and low to moderate levels of
pollutants.
10.5.1 Mix the sample thoroughly using a clean
spatula.
10.5.2 Weigh 5 * 1 grams of sample into a purging
vessel (Figure 2). Record the weight to
three significant figures.
10.5.3 Add 5.0 ± 0.1 ml of reagent water to the
vessel.
10.5.4 Using a metal spatula, break up any lumps
of sample to disperse the sample in the
water.
10.5.5 Add an appropriate amount of the labeled
compound spiking solution (Section 6.6) to
the sample in the purge vessel. Place a
cap on the purging vessel and and shake
vigorously to further disperse the sample.
Attach the purge vessel to the purging
device, and purge the sample per Section
10.7.
10.6 Samples containing one percent solids or
greater, and high levels of pollutants, or
samples requiring dilution by a factor of
more than 100 (see Section 13.4).
10.6.1 Nix the sample thoroughly using a clean
spatula.
10.6.2 Weigh 5 t 1 grams of sample into a
calibrated 15 - 25 mL centrifuge tube.
: Record the weight of the sample to three
significant figures.
10.6.3 Add 10.0 ml of methanol to the centrifuge
tube. Cap the tube and shake it
vigorously for 15 - 20 seconds to disperse
the sample in the methanol. Allow the
sample to settle in the tube. If
necessary, centrifuge the sample to settle
suspended particles.
10.6.4 Remove approximately 0.1 percent of the
volume of the supernatant methanol using a
15 - 25 uL syringe. This volume will be
in the range of 10 - 15 uL.
10.6.5 Add this volume of the methanol extract to
5 ml reagent water in a 5 ml syringe, and
analyze per Section 10.4.1.
10.6.6 For further dilutions, dilute 1 mL of the
supernatant methanol (10.6.4) to 10 mL,
100 mL, 1000 mL, etc., in reagent water.
Remove a volume of this methanol
extract/reagent water mixture equivalent
to the volume in Step 10.6.4, add it to 5
mL reagent water in a 5 mL syringe, and
analyze per Section 10.4.1.
19
-------
10.7 Purg* the sample for 11.0 ± 0.1 minutes at
20 - 25 "C for samples containing less
than ont percent solids. Purge samples
containing one percent solids or greater
at 40 * 2 *C. If the compounds in Table 2
that do not purge at 20 - 40 °Q are to be
determined, a purge temperature of 80 ± 5
•C is used.
10.8 After the 11 minute purge time, attach the
trap to the chrometograph and set the
purg« and trap apparatus to the desorb
mode (Figure 5). Desorb the trapped
compounds into the GC column by heating
the trap to 170 - 180 °C while
backflushing with carrier gas at 20 - 60
wL/min for four minutes. Start HS data
acquisition upon start of the desorb
cycle, and start the GC column temperature
program 3 minutes later. Table 3
summarizes the recommended operating
conditions for the gas chromatograph.
Included in this table are retention times
and minimum levels that can be achieved
under these conditions. An example of the
separations achieved by the column listed
is shown in Figure 9. Other columns may
b* used provided the requirements in
Section 8 are met. If the priority
pollutant gases produce GC peaks so broad
that the precision and recovery
specifications (Section 8.2) cannot be
met', the column may be cooled to ambient
or subanbient temperatures .to sharpen
these peaks.
10.9 After desorbing this sample for four
minutes, recondition the trap by purging
with purge gas while maintaining the trap
temperature at 170 - 180 °C. After
approximately seven minutes, turn off the
trap heater to stop the gas flow through
the trap. When cool, the trap is ready
for the next sample.
10.10 While analysis of the desorbed compounds
proceeds, remove and clean the purge
device. Rinse with tap water, clean with
detergent and water, rinse with tap and
distilled water, and dry for one hour
minimum in an oven at a temperature
greater than 150 *C.
11 SYSTEH PERFORMANCE
11.1 At the beginning of each 8 hr shift during
which analyses arc performed, system
calibration and performance shall be
verified for the pollutants and labeled
compounds CTable 1). For these tests,
analysis of the aqueous performance
standard (Section 6.7.2) shall be used to
verify oil performance criteria.
Adjustment and/or recalibration (per
Section 7) shall be performed until all
performance criteria are met. Only after
all performance criteria are met may
blanks and samples be analyzed.
11.2 BFB spectrum validity—the criteria in
Table 4 shall be met.
11.3 Retention times—the absolute retention
times of the internal standards shall be
as follows: bromochloromethane: 653 - 782
seconds; 2-bromo-1-chloropropane: 1270 -
1369 seconds; 1,4-dichlorobutane: 1510 -
1605 seconds. The relative retention
times of all pollutants and labeled
compounds shall fall within the limits
given in Table 3.
11.4 GC resolution—the valley height between
toluene and toluene-dg (at m/z 91 and 99
plotted on the same graph) shall be less
than 10 percent of the taller of the two
peaks.
11.5 Calibration verification and on-going
precision and accuracy -- compute the
concentration of each pollutant (Table 1)
by isotope dilution (Section 7.4) for
those compounds which have labeled
analogs. Compute the concentration of
each pollutant which has no labeled analog
by the internal standard method (Section
7.5). Compute the concentrations of the
labeled compounds themselves by the
internal standard method. These
concentrations are computed based on the
calibration data determined in Section 7.
11.5.1 For each pollutant and labeled compound,
compare the concentration with the
corresponding limit for on-going accuracy
in Table 6.
If all compounds meet the acceptance
criteria, system performance is acceptable
and analysis of blanks and samples may
continue. If any individual value falls
outside the range given, system
performance is unacceptable for that
compound.
20
-------
NOTE: The large number of compounds in
Table 6 present a substantial probability
that one or more Mill fail the acceptance
criteria when all compounds are analyzed.
To determine if the analytical system is
out of control, or if the failure may be
attributed to probability, proceed as
follows:
Develop a statement of accuracy for each
pollutant and labeled compound by
calculating the average percent recovery
(R) and the standard deviation of percent
recovery (sr). Express .the accuracy as a
recovery interval from R - 2s to R + 2s .
For example, if R = 95% and s = 5%, the
accuracy is 85 - 105 percent.
11.5.1.1 Analyze a second aliquot of the aqueous
performance standard (Section 6.7.2).
11.5.1.2 Compute the concentration for only those
compounds which failed the first test
(Section 11.5.1). If these compounds now
pass, system performance is acceptable for
all compounds, and analyses of blanks and
samples may proceed. If, however, any of
the compounds fail again, the measurement
system is not performing properly for
these compounds. In this event, locate
and correct the problem or recalibrate the
system (Section 7), and repeat the entire
test (Section 11.1) for all compounds.
11.5.2 Add results which pass the specification
in 11.5.1.2 to initial (Section 8.2) and
previous on-going data. Update QC charts
to form a graphic representation of
laboratory performance (Figure 8).
8
*• 120,000
W
Se
DC
<
*:
100,000
80,000
TOLUENE-D,
• * *
' • * * *
12 3456789 10
ANALYSIS NUMBER
If
II
0.90 -
TOLUENE
• • *~ t t • "
- • *
6/1 6/1 611 6/1 6/2 6/2 6/3 6/3 6/4 6/5
DATE ANALYZED
FIGURES Quality Control Charts Showing Area
(top graph) and Relative Response of Toluene to
Toluene-da (lower graph) Plotted as Function of
Time or Analysis Number
12 QUALITATIVE DETERMINATION
Identification is accomplished by
comparison of data from analysis of a
sample or blank with data stored in the
mass spectral libraries. For compounds
for which the relative retention times and
mass spectra are known, identification is
confirmed per Sections 12.1 and 12.2. For
unidentified GC peaks, the spectrum is
compared to spectra in the EPA/NIH mass
\ spectral file per Section 12.3.
12.1 Labeled compounds and pollutants having no
labeled analog (Tables 1 and 2):
12.1.1 The signals for all characteristic m/z's
stored in the spectral library (Section
7.2.3) shall be present and shall maximize
within the same two consecutive scans.
12.1.2 Either (1) the background corrected EICP
areas, or (2), the corrected relative
intensities of the mass Spectral peaks at
the GC peak maximum shall agree within a
factor of two (0.5 to 2 times) for all
masses stored in the library.
12.1.3 In order for the compounds for which the
system has been calibrated (Table 1) to be
identified, their relative retention times
shall be within the retention time windows
specified in Table 3.
12.1.4 The system has not been calibrated for the
compounds listed in Table 2, however, the
relative retention times and mass spectra
of these compounds are known. Therefore,
for a compound in Table 2 to be
identified, its relative retention time
must fall within a retention time window
of ± 60 seconds or ± 20 scans (whichever
is greater) of the nominal retention time
of the compound specified in Table 3.
12.2 Pollutants having a labeled analog (Table
1):
21
-------
12.2.1 The signals for all characteristic m/z's
stored in the spectral library (Section
7.2.3) shall be present and shall maximize
within the same two consecutive scans.
12.2.2 Either (1) the background corrected EICP
areas, or (2) th« corrected relative
intensities of the mass spectral peaks at
the GC peak maximum shall agree within a
factor of two for all masses stored in the
spectral library.
12.2.3 The relative retention time between the
pollutant and its labeled analog shall be
within the windows specified in Table 3.
12.3 Unidentified GC peaks
12.3.1 The signals for m/z's specific to a GC
peak shall all maximize within the same
two consecutive scans.
12.3.2 Either (1) the background corrected EICP
areas, or (2) the corrected relativ*
intensities of the BOSS spectral peaks at
the GC peak maximum shall agree within a
factor of two with the masses stored in
the EPA/HIH Mass Spectral File.
12.4 The m/z's present in the sample mass
spectrum that are not present in the
reference mass spectrum shall be accounted
for by contaminant or background ions. If
the sample mass spectrum is contaminated,
or if identification is ambiguous, an
experienced spectrometrist (Section 1.4)
is to determine the presence or absence of
the compound.
13 QUANTITATIVE DETERMINATION
13.1 Isotope dilution -- Because the pollutant
and its labeled analog exhibit the same
effects upon purging, desorption, and gas
chromatography, correction for recovery of
the pollutant can be made by adding a
known amount of a labeled compound to
every sample prior to purging. Relative
response (RR) values for sample mixtures
are used in conjunction with the
calibration curves described in Section
7.4 to determine concentrations directly,
so long as labeled compound spiking levels
are constant. For the toluene example
given in Figure 7 (Section 7.4.3), RR
would be equal to 1.174. For this RR
value, the toluene calibration curve given
in Figure 6 indicates a concentration of
31.8 ug/L.
13.2 Internal standard--for the compounds for
which the system was calibrated (Table 1)
according to Section 7.5, use the response
factor determined during the calibration
to calculate the concentration from the
following equation.
Concentration = (A x C. )
(A.g x RF)
where the terms are as defined in Section
7.5.1. For the compounds for which the
system was not calibrated (Table Z), use
the response factors in Table 5 to
calculate the concentration.
13.3 The concentration of the pollutant in the
solid phase of the sample is computed
using the concentration of the pollutant
detected in the aqueous solution, as
follows:
Concentration in solid (ug/kg) =
0.005 L x aqueous cone (ug/L)
0.01 x X solids (g)
where "% solids" is from Section 10.1.3.
13.4 Dilution of samples—if the EICP area at
the quantitation m/z exceeds the
calibration range of the system, samples
are diluted by successive factors of 10
until the area is within the calibration
range.
13.4.1 For aqueous samples, bring 0.50 ml, 0.050
ml, 0.0030 ml etc. to 5 mL volume with
reagent water and analyze per Section
10.4.
13.4.2 For samples containing high solids,
substitute 0.50 or 0.050 gram in Section
10.5.2 to achieve a factor of 10 or 100
dilution, respectively.
13.4.3 If dilution of high solids samples by
greater than a factor of 100 is required,
then extract the sample with methanol, as
described in Section 10.6.
13.5 Dilution of samples containing high
concentrations of compounds not in Table 1
-- When the EICP area of the quantitat ion
22
-------
m/z of a compound to be identified per
Section 12.3 exceeds the linear range of
the GCNS system, or when any peak in the
mass spectrum is saturated, dilute the
sample per Sections 13.4.1-13.4.3.
13.6 Report results for all pollutants, labeled
compounds, and tentatively identified
compounds found in all standards, blanks,
and samples to three significant figures.
For samples containing less than one
percent solids, the units are ug/L, and
ug/kg for undiluted samples containing one
percent solids or greater.
13.6.1 Results for samples which have been
diluted are reported at the least dilute
level at which the area at the
quantisation m/z is within the calibration
range (Section 13.4), or at which no m/z
in the spectrum is saturated (Section
13.5). For compounds having a labeled
analog, results are reported at the least
dilute level at which the area at the
quantitation m/z is within the calibration
range (Section 13.4) and the labeled
compound recovery is within the normal
range for the method (Section 14.2).
14 ANALYSIS OF COMPLEX SAMPLES
14.1 Some samples may contain high levels
(>1000 ug/kg) of the compounds of fnterest
and of interfering compounds. Some
• samples will foam excessively when purged.
Others will overload the trap or the GC
column.
14.2 When the recovery of any labeled compound
is outside the range given in Table 6,
dilute 0.5 mL of samples containing less
than one percent solids, or 0.5 gram of
samples containing one percent solids or
greater, wfth 4.5 mL of reagent water and
analyze this diluted sample. If the
recovery remains outside of the range for
this diluted sample, the aqueous
performance standard shall be analyzed
(Section 11) and calibration verified
(Section 11.5). If the recovery for the
labeled compound in the aqueous
performance standard is outside the range
given in Table 6, the analytical system is
out of control. In this case, the
instrument shall be repaired, the
performance specifications in Section 11
shall be met, and the analysis of the
undiluted sample shall be repeated.
If the recovery for the aqueous
performance standard is within the range
given in Table 6, then the method does not
apply to the sample being analyzed, and
the result may not be reported for
regulatory compliance purposes.
14.3 When a high level of the pollutant is
present, reverse search computer programs
may misinterpret the spectrum of chromato-
graphically unresolved pollutant and
labeled compound pairs with overlapping
spectra. Examine each chromatogram for
peaks greater than the height of the
internal standard peaks. These peaks can
obscure the compounds of interest.
15 METHOD PERFORMANCE
15.1 The specifications for this method were
taken from the inter-laboratory validation
of EPA Method 624 (Reference 10). Method
1624 has been shown to yield slightly
better performance on treated effluents
than method 624. Results of initial tests
of this method at a purge temperature of
80 °C can be found in Reference 11 and
results of initial tests of this method on
municipal sludge can be found in Reference
12.
15.2 A chromatogram of the 20 ug/L aqueous
performance standards (Sections 6.7.2 and
11.1) is shown in Figure 9.
23
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MASS CHWHATOCRAH DATA: UOAI01945 It
83/81/84 23185:96 CALI: WJAID1945 11
SAHPLEl UO,S,OPR,8ee29,ee,U,NAsHft,HftS
OWOS.t 16248,3.BH,2tt1,3t43,45-248l8,15i24B,2eil./mNS
RANGE: C 1,1299 LABEL: N 6, 4.0 QUAH: A 8, 1.8 J
SCANS 1 TO 1208
8 BASE: U 29, 3
222976.
27:28
1088
34n 18
1288 SCAN
41:88 TIME
FIGURE 9 Chromatogram of Aqueous Performance Standard
24
-------
REFERENCES
"Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass
Spectrometry Equipment; and Laboratories,"
USEPA, EMSL Cincinnati, OH 45268, EPA-
600/4-80-025 (April 1980).
Bellar, T. A. and Lichtenberg, J. J.,
"Journal American • Water Works Assoc-
iation," 66, 739 (1974).
Bellar, T. A. and Lichtenberg, J. J.,
"Semi-automated Headspace Analysis of
Drinking Waters and Industrial Waters for
Purgeable Volatile Organic Compounds," in
Measurement of Organic Pollutants in Water
and Uastewater. c. E. VanHall, ed.,
American Society for Testing Materials,
Philadelphia, PA, Special Technical
Publication 686, (1978).
National Standard Reference Data System,
"Mass Spectral Tape Format", US National
Bureau of Standards (1979 and later
attachments).
"Working with Carcinogens," DHEW, PHS,
N10SH, Publication 77-206 (1977).
"OSHA Safety and Health Standards, General
Industry," 29 CFR 1910, OSHA 2206. (1976).
"Safety in Academic Chemistry Laborato-
ries," American Chemical Society Publica-
tion, Committee on Chemical Safety (1979).
8. "Handbook of Analytical Quality Control in
Water and Wastewater Laboratories," USEPA,
ENSL Cincinnati, OH 45268, EPA-4-79-019
(March 1979).
9. "Methods 330.4 and 330.5 for Total
Residual Chlorine," USEPA, EMSL Cincin-
nati, OH 45268, EPA-4-79-020 (March 1979).
10. "Method 624--Purgeables", 40 CFR Part 136
(49 FR 43234), 26 October 1984.
11. "Narrative for SAS 106: Development of an
Isotope Dilution GC/MS Method for Hot
Purge and Trap Volatiles Analysis", S-
CUBED Division of Maxwell Laboratories,
Inc., Prepared for W. A. Telliard,
Industrial Technology Division (UH-552),
USEPA, 401 M St SW, Washington DC 20460
(July 1986).
12. Colby, Bruce N. and Ryan, Philip W.,
"initial Evaluation of Methods 1634 and
1635 for the Analysis of Municipal
Wastewater Treatment Sludges by Isotope
Dilution GCMS", Pacific Analytical Inc.,
Prepared for W. A. Telliard, Industrial
Technology Division (WH-552), USEPA, 401 M
St SW, Washington DC 20460 (July 1986).
25
-------
Appendix A .
Mass Spectra in the Form of Mass/Intensity Lists
532 allyl alcohol
pi/; int. m/z
42 30 43
56 58 57
533 carbon disulfide
m/z fnt. ro/z
44 282 46
int.
39
1000
int.
10
m/z
44
58
m/z
64
int.
232
300
fnt.
14
m/z
45
61
m/z
76
int.
12
15
int.
1000
mil
53
m/z
77
int.
13
ioL,
27
m/z int.
55 59
m/z int.
78 82
534 2-chloro-1,3-butadiene (chloroprene)
m/z int. m£z
48 21 49
54 41 61
87 12 88
535 chloroacetonftrile
m/z fnt. m/z
47 135 48
74 43 75
536 3-chloropropene
p/g fnt, m/g
35 39 36
49 176 51
76 1000 77
537 crotonaldehyde
mfz fnt. m£2.
35 26 40
50 40 51
69 511 70
int.
91
30
452
int.
1000
884
int.
40
64
74
int.
28
20
1000
m/z
50
62
89
mil
49
76
m/z
40
52
78
m/z
42
52
71
int.
223
54
22
int.
88
39
int.
44
31
324
int.
339
21
43
51
63
90
att
50
77
m/z
42
61
m/z
43
53
int.
246
11
137
int.
294
278
int.
206
29
int.
48
31
52
64
m/z
51
m/z
47
73
m/z
44
55
int.
241
16
int.
12
int.
40
22
int.
335
55
53 1000
73 21
m/t' int.
73 22
m/z fnt.
58 35
75 138
m/z int.
49 27
68 24
538 1,2-dibromoethane (EDB)
m/z fnt. f>/z
79 50 80
105 32 106
186 13 188
539 dibroaxxoethans
m/z; fnt. m/z
43 99 44
91 142 92
172 375 173
540 trans-1,4-dichloro-
p/S fnt. m/z
49 166 50
62 286 64
90 93 91
fnt.
13
29
27
int.
101
61
14
2-butene
int.
171
91
129
m/z
31
107
190
m/z
45
93
174
m/z
51
75
124
fnt.
51
1000
13
int.
30
1000
719
int.
289
1000
138
mH
82
108
atz
79
94
175
m/z
52
77
126
int.
15
38
int.
184
64
12
int.
85
323
86
m/z
93
109
mil
80
95
176
m/z
53
88
128
int.
54
922
int.
35
875
342
int.
878
246
12
m/z int.
95 42
110 19
m/z fnt.
81 175
160 18
,
«/z int.
54 273
89 415
26
-------
Appendix A (continued)
Mass Spectra in the Form of Mass/Intensity Lists
541 1,3-dichloropropane
m/z int. m/z
40 15 42
61 18 62
77 46 78
542 cis-1,3-dichloropropene
m/z int. m/z
37 262 38
77 328 110
543 ethyl cyanide
m/z int. m/z
44 115 50
55 193
544 ethyl methacrylate
m/z int. . m/z
42 127 43
69 1000 70
96 17 99
int.
44
22
310
int.
269
254
int.
34
ia$i
48
83
93
m/z
47
63
79
m/z
39
112
m/z.
51
m/Z
45
71
113
int.
19
131
12
int.
998
161
int.
166
int.
155
25
11
Si*
48
65
m/z
49
B/z.
52
m/s
55
85
114
int.
20
38
int.
596
int.
190
int.
32
14
119
m/z
49
75
m/z
51
m/z.
53
m/z
58
86
int.
193
47
int.
189
int.
127
int.
39
169
m/z
51
76
m/z
75
m/z
54
m/z
68
87
int.
55
1000
int.
1000
int.
1000
int.
60
21
545 2-hexanone (methyl butyl ketone)
M2. int. m/z
42 61 43
59 21 71
546 iodomethane
m/z int. m/z
44 57 127
142 1000 143
547 isobutyl alcohol
ffl^z int. m/z
34 21 35
43 1000 44
59 25 73
548 methacrylonitrile
m/z Int., m/z
38 24 39
51 214 52
65 55 66
549 methyl methacrylate
SS/z int.. m/z
42 127 43
59 124 68
98 20 99
intt
1000
36
int.
323
12
jnt.
13
42
12
int.
21
446
400
int.
52
28
89
B££
44
85
ail
128
i££
36
45
7*
B&
41
53
67
l£
45
69
100
iht;
24
37
int.
17
Int.
13
21
63
int.
26
19
1000
int.
48
1000
442
B/I
55
100
a&
139
ate
37
55
B/z
42
62
68
912.
53
70
101
int.
12
56
int.
39
int.
11
40
lot,.
100
24
51
int.
30
51
22
ffl/£
57
B/z
140
m/z
39
56
m/z
49
63
5
m/z
55
82
int.
130
int.
34
int.
10
37
int.
19
59
int.
100
26
m/z
58
m/z
141
m/z
42
57
m/z
50
64
m/z
56
85
int.
382
int.
120
int.
575
21
int.
60
136
int.
49
45
27
-------
Appendix A (continued)
Mass Spectra in the Fora of Mass/Intensity Lists
550 4-BKthyt-2-F
m/z int.
42 69
57 205
100 94
Mntanone (methyl isobutyl ketone; MI8K)
,q/z .int.. m/z int. m/z int. m/z int.. m/z int.
43 1000 44 54 53 11 55 15 56 13
58 346 59 20 67 12 69 10 85 96
551 1,1,1,2-tetrachlorosthane
m/z fnt. p/z jnfo, m/z in£.. ate int.. a,£z int.. m^z int..
47 144 49 163 60 303 61 330 62 98 82 45
64 31 95 416 96 152 97 .270 98 84 117 804
121 236 131 1000 133 955 135 301
552 trfchlorofluoromethane
m/z Int. m/z jpJU. *£* Ms. S& Ms.
44 95 47 153 49 43 51 21
68 53 82 40 84 28 101 1000
105 102 117 16 119 14
52
102
lots.
14
10
66
103
int.
162
671
553 1,2,3-tHchloropropane
•S Hfe ^
76 38 77
99 103 110
302
265
83
111
23
28
96
112
29
164
97
114
166
25
98
20
554 vinyl acetate
B/Z int. a& tot*.
36 5 42 103
ioS*
43 1000
44
ios*.
70
aZs
45
m/z
86
57
951 M-xylcne
p/i int.
65 62
77
lots.
124
91
int.
1000
105
int.
245
106 580
int.
951 o- + p-xylene
m/z int.
51 88 77
131
91
int.
1000
105
int.
229
i& int.
106 515
m/z
int.
28
-------
Method 1625 Revision C June 1989
Semivolatile Organic Compounds by Isotope Dilution GCMS
1 SCOPE AM) APPLICATION
1.1 This method is designed to meet the survey
requirements of the USEPA ITD. The method
is used to determine the semivolatile
toxic organic pollutants associated with
the Clean Water Act (as amended 1987); the
Resource Conservation and Recovery Act (as
amended 1986); the Comprehensive Environ-
mental Response, Compensation and
Liability Act (as amended 1986); and other
compounds amenable to extraction and
analysis by capillary column gas
chromatography-mass spectrometry (GCMS).
1.2 The chemical compounds listed in Tables 1
through 4 may be determined in waters.
soils, and municipal sludges by the
method.
1.3 The detection limits of the method are
usually dependent on the level of
interferences rather than instrumental
limitations. The limits in Tables 5 and 6
typify the minimum quantities that can be
detected with no interferences present.
1.4 The GCMS portions of the method are for
use only by analysts experienced with GCMS
or under the close supervision of such
qualified persons. Laboratories unfamil-
iar with analysis of environmental samples
by GCMS should run the performance tests
in Reference 1 before beginning.
Table 1
BASE/NEUTRAL EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES
Pollutant
Labeled Compound
Comoound
acenaphthene
acenaphthylenc
anthracene
benzidine
benzo(a)anthracene
benzo(b)fluoranthene
benzo(k)f luoranthene
benzo(a)pyrene
benzo(gh i )perylene
biphenyl (Appendix C)
bis(2-chloroethyl) ether
bis(2-chloroethoxy)methane
bis(2-chloroisopropyl) ether
bis(2-ethylhexyl) phthalate
4-bromophenyl phenyl ether
butyl benzyl phthalate
n-C10 (Appendix C)
n-C12 (Appendix C)
n-C14 (Appendix C)
n-C16 (Appendix C)
h-C18 (Appendix C)
n-C20 (Appendix C)
n-C22 (Appendix C)
n-C24 (Appendix C)
n-C26 (Appendix C)
n-C28 (Appendix C)
n-C30 (Appendix C)
Storet
34205
34200
34220
39120
34526
34230
34242
34247
34521
81513
34273
34278
34283
39100
34636
34292
77427
77588
77691
77757
77804
77830
77859
77886
77901
78116
78117
CAS Registry
83-32-9
208-96-8
120-12-7
92-87-5
56-55-3
205-99-2
207-08-9
50-32-8
191-24-2
92-52-4
111-44-4
111-91-1
108-60-1
117-81-7
101-55-3
85-68-7
124-18-5
112-40-3
629-59-4
544-76-3
593-45-3
112-95-8
629-97-0
646-31-1
630-01-3
630-02-4
638-68-6
EPA-EGD
001 B
0778
078 B
005 B
072 B
074 B
075 B
073 B
079 B
512 B
018 B
043 B
042 B
066 B
041 B
067 B
517 B
506 B
518 B
519 B
520 B
521 B
522 B
523 B
524 B
525 B
526 B
NPDES
001 B
002 B
003 B
004 B
005 B
007 B
009 B
006 B
008 B
011 B
010 B
012 B
013 B
014 B
015 B
618 B
620 B
622 B
624 B
625 B
d.
O
d10
1U
d.
O
d12
Ic
d12
1C
d12
Ic
d.2
1C
d10
IU
V
O
d.
O
d12
1C
d.
-------
Table 1 (continued)
lASE/NEUTRAL EXTRACTABLE COMPOUNDS DETERMINED SY GCMS USING ISOTOPE DILUTION
Pollutant
AIID INTERNAL STANDARD TECHNIQUES
Labeled Compound
carbazole (4c)
2-chloronaphthalene
4-chlorophenyl phenyl ether
chryaene
p-cyraene (Appendix C)
dibenzo(a,h)anthracene
dibemofuran (Appendix C & 4c)
dtbenzothiophene (Synfuel)
di-n-butyl phthalate
1 ,2-dichlorobenzene
1,3-dtchlorobenzene
1 ,4-dichlorobenzene
3,3'-dichlorobenzidine
diethyl phthalate
2,4-diiaethylphenol
dimethyl phthalate
2,4-dlnltrotoluene
2,6-dinftrotoluene
di-n-octyl phthalate
diphenylamine (Appendix C)
diphenyl ether (Appendix C)
1 ,2-diphenylhydrazine
fluoranthene
fluorene
h exnch 1 orobenzene
hexnch lorobutadi ene
hexachloroethane
hexaehlorocyclopentadiene
indenod ,2,3-cd)pyrene
Isophorone
naphthalene
beta-naphthylaraine (Appendix C)
nitrobenzene
H-nitroiodinethylamine
H-nitrotodi-n-proplyamine
M*nitrotodiphenylamine
phenanthrene
phenol
alpha-picoline (Synfuel)
pyrene
styrene (Appendix C)
alpha-terpineol (Appendix C)
1,2,3-trichlorobenzene (4c)
1,2,4-trichlorobenzene
Storet
77571
34581
34641
34320
77356
34556
81302
77639
391.10
34536
34566
34571
34631
34336
34606
34341
34611
34626
34596
77579
77587
34346
34376
34381
39700
34391
34396
34386
34403
34408
34696
82553
34447
34438
34428
34433
34461
34694
77088
34469
77128
77493
77613
34551
CAS Registry
86-74-8
91-58-7
7005-72-3
218-01-9
99-87-6
53-70-3
132-64-9
132-65-0
84-74-2
95-50-1
541-73-1
106-46-7
91-94-1
84-66-2
105-67-9
131-11-3
121-14-2
606-20-2
117-84-0
122-39-4
101-84-8
122-66-7
206-44-0
86-73-7
118-74-1
87-68-3
67-72-1
77-47-4
193-39-5
78-59-1
91-20-3
91-59-8
98-95-3
62-75-9
621-64-7
86-30-6
85-01-8
108-95-2
109-06-8
129-00-0
100-42-5
98-55-5
87-61-6
120-82-1
EPA-EGD
528 B
020 B
040 B
076 B
513 B
082 B
505 B
504 B
068 B
025 B
026 B
027 B
028 B
070 B
034 A
071 B
035 B
036 B
069 B
507 B
508 B
037 B
039 B
080 B
009 B
052 B
012 B
053 B
083 B
054 B
055 B
502 B
056 B
061 B
063 B
062 B
081 B
065 A
503 B
084 B
510 B
509 B
529 B
008 B
NPDES
016 B
017 B
018 B
019 B
026 B
020 B
021 B
022 B
023 B
024 B
003 A
025 B
027 B
028 B
029 B
030 B
031 B
032 B
033 B
034 B
036 B
035 B
057 B
038 B
039 B
040 B
041 B
042 B
043 B
044 B
010 A
045 B
046 B
Analog
d8
*f
ds
d12
d14
d14
d8
d8
d4
d4
d4
d4
d6
d4
"3
d4
««S
"3
d4
d10
d10
d10
d10
£10
'•3r
,1 &
13C
«T 4
1V
1\
d8
d8
d7
ds
d6
d14
d6
d10
d5
d7
d10
d5
^
"3
"3
CAS Registry
38537-24-5
93951-84-9
93951-85-0
1719-03-5
93952-03-5
13250-98-1
93952-04-6
33262-29-2
93952-11-5
2199-69-1
2199-70-4
3855-82-1
93951-91-8
93952-12-6
93951-75-8
93951-89-4
93951-68-9
93951-90-7
93952-13-7
37055-51-9
93952-05-7
93951-92-9
93951-69-0
81103-79-9
93952-14-8
93951-70-3
93952-15-9
93951-71-4
93952-16-0
1146-65-2
93951-94-1
4165-60-0
17829-05-9
93951-96-3
93951-95-2
1517-22-2
4165-62-2
93951-93-0
1718-52-1
5161-29-5
93952-06-8
3907-98-0
2199-72-6
EPA-EGD
628 B
220 B
240 B
276 B
613 B
282 B
605 B
604 B
268 B
225 B
226 B
227 B
228 B
270 B
234 A
271 B
235 B
236 B
269 B
607 B
608 B
237 B
231 B
280 B
209 B
252 B
212 B
253 B
254 B
255 B
602 B
256 B
261 B
263 B
262 B
281 B
265 A
603 B
284 B
610 B
609 B
629 B
208 B
30
-------
Table 2
ACID EXTRACTABLE COMPOUNDS DETERMINED BY GCMS USING ISOTOPE DILUTION AND INTERNAL STANDARD TECHNIQUES
Pollutant
Labeled Compound
CofflBOund
4-chloro-3-methylphenol
2-chlorophenol
2,4-dichlorophenol
2,4-dinitrophenol
2-methyl-4,6-dinitrophenol
2-nitrophenol
4-nitrophenol
pentachlorophenol
2,3,6-trichlorophenol (Ac)
2,4,5- trichlorophenol <4c)
2,4,6-trichlorophenol
Storet
34452
34586
34601
34616
34657
34591
34646
39032
77688
34621
CAS Registry
59-50-7
95-57-8
120-83-2
51-28-5
534-52-1
88-75-5
100-02-7
87-86-5
933-75-5
95-95-4
88-06-2
EPA-EGD NPDES Analog
022 A 008 d,
024 A 001
031 A 002
059 A 005
060
057
058
064
530
531
021
004
006
007
009
C. -
d.
•»
dj
d.
£
dj
d.
H
<*A
13 *
c*
o
d.
?
011 A d2
CAS Registry
93951-72-5
93951-73-6
93951-74-7
93951-77-0
93951-76-9
93951-75-1
93951-79-2
85380-74-1
93951-81-6
93951-82-7
93951-80-5
222 A
224 A
231 A
259 A
260 A
257 A
258 A
264 A
630 A
631 A
221 A
Table 3
BASE/NEUTRAL EXTRACTABLE COMPOUNDS TO BE DETERMINED BY REVERSE SEARCH AND QUANTITATION
USING KNOWN RETENTION TIMES. RESPONSE FACTORS, REFERENCE COMPOUND, AND MASS SPECTRA
EGO
No.
555
556
557
558
559
560
561
562
563
564
565
566
567
568
569
570
571
572
573
574
575
576
577
578
579
580
581
582
583
584
585
586
Compound
acetophenone
4-aminobiphenyl
aniline
o-anisidine
aramite
benzanthrone
1 ,3-benzenediol (resorcinol )
benzenethiol
2,3-benzofluorene
benzyl alcohol
2-bromochlorobenzene
3-bromochlorobenzene
4-chloro-2-nitroaniline
, 5-chloro-o-toluidine
4-chloroaniline
3-chloronitrobenzene
o-cresol
crotoxyphos
2,6-di -tort-butyl -p-benzoquinone
2,4-diaminotoluene
1,2-dibromo-3-chloropropane
2,6-dichloro-4-nitroaniline
1,3-dichloro-2-propanol
2,3-di chloroani I ine
2,3-dichloronitro-benzene
1 ,2:3,4-diepoxybutane
3,3' -dimethoxybenzidine
dimethyl sulfone
p-dimethylamino-azobenzene
7, 12-dimethylbenz- (a)anthracene
N.N-dimethylformamide
3,6-dimethylphenanthrene
CAS
Registry
98-86-2
92-67-1
62-53-3
90-04-0
140-57-8
82-05-3
108-46-3
108-98-5
243-17-4
100-51-6
694-80-4
108-37-2
89-63-4
95-79-4
106-47-8
121-73-3
95-48-7
7700-17-6
719-22-2
95-80-7
96-12-8
99-30-9
96-23-1
608-27-5
3209-22-1
1464-53-5
119-90-4
67-71-0
60-11-7
57-97-6
68-12-2
1576-67-6
EGO
No.
587
588
589
590
591
592
593
594
595
596
597
598
599
900
901
902
903
904
905
906
907
908
909
910
911
912
913
914
915
916
917
918
Compound
1 ,4-dinitrobenzene
diphenyldisulfide
ethyl methanesulfonate
ethylenethiourea
ethynylestradiol3-methyl ether
hexach I oropropene
2- isopropylnaphthalene
isosafrole
longifolene
malachite green
methapyrilene
methyl methanesulfonate
2-methylbenzothioazole
3 -methyl cho I anthrene
4,4' -methylene-bis(2-chloroani 1 ine)
4,5-methylene-phenanthrene
1 -methyl f luorene
2-methylnaphtha lene
1 -methylphenanthrene
2- (methyl thio)-benzothiazole
1 ,5-naphthalenediamine
1,4-naphthoquinone
alpha-naphthylamine
5-nitro-o-toluidine
2-nitroaniline
3-nitroaniline
4-nitroaniline
4-nitrobiphenyl
N-nitrosodi-n-butylamine
N-nitrosodiethylamine
CAS
Registry
100-25-4
882-33-7
62-50-0
96-45-7
72-33-3
1888-71-7
2027-17-0
120-58-1
475-20-7
569-64-2
91-80-5
66-27-3
120-75-2
56-49-5
101-14-4
203-64-5
1730-37-6
91-57-6
832-69-9
615-22-5
2243-62-1
130-15-4
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
92-93-3
924-16-3
55-18-5
N-nitrosomethyl-ethylamine 10595-95-6
N-nitrosomethyl-phenylamine
614-00-6
31
-------
TabU 3 (continued)
BASE/HGUTRAU EXTRACTABLE COMPOUNDS TO BE DETERMINED
St REVERSE SEARCH AND QUANTITATION USING KNOWN
RETENTION TIMES, RESPONSE FACTORS, REFERENCE
COMPOUND, AND MASS SPECTRA
Table 4
ACID EXTRACTABLE COMPOUNDS TO BE DETERMINED BY
REVERSE SEARCH AND QUANTITATION USING KNOWN RETENTION
TIMES, RESPONSE FACTORS, REFERENCE COMPOUND, AND MASS
SPECTRA
EGO
Ho.
919
920
921
922
923
924
925
926
927
928
929
930
931
932
933
934
935
936
937
938
939
940
941
942
Compound
N-ni trosoroorpholfne
H-n!trosopip«ridine
pentachlorobenzene
pentachlorocthme
ptntamethylbenzene
parylen*
phtnacttin
phenothiazine
1 -phenylnaphthalene
2-phenylnaphthalene
pronamide
pyridine
safrole
squalene
1 ,2,4,5-t«tra-chlorobenzene
tManaphthent(2,3-benzothiophene)
thtoacatamid*
thfoxanthone
o-toluidine
1,2,3-trimethoxybenzene
2,4,5-trimethylaniline
triphenylene
trlpropyleneglycolraethyl ether
1,3,5-trithiene
CAS
Registry
59-89-2
100-75-4
608-93-5
76-01-7
700-12-9
198-55-0
62-44-2
92-84-2
605-02-7
612-94-2
23950-58-5
110-86-1
94-59-7
7683-64C9
95-94-3
95-15-8
62-55-5
492-22-8
95-53-4
634-36-6
137-17-7
217-59-4
20324-33-8
291-21-4
2 SUMMARY OF METHOD
2.1 The percent solids content of a sample is
determined. Stable isotopically labeled
analogs of the compounds of interest are
added to the sample. If the solids content
is lest than one percent, a one liter
sample is extracted at pH 12 - 13, then at
pH <2 with raethytene chloride using
continuous extraction techniques. If the
solid* content is 30 percent percent or
less, the sample is diluted to one,percent
solids with reagent water, homogenized
ultrasonically, and extracted at pH 12-13,
then at pH <2 with methylene chloride
using continuous extraction techniques. If
the solids content is greater than 30
percent, the sample is extracted using
ultrasonic techniques. Each extract is
dried over sodium sulfate, concentrated to
a volume of five mL, cleaned up using gel
permeation chromatography (GPC), if
EGO
HO.
943
944
945
946
947
948
Compound
benzoic acid
p-cresol
3,5-dibromo-
4-hydroxybenzonitri le
2,6-dichlorophenol
hexanoic acid
2,3,4,6-tetrachlorophenol
tAS
Registry
65-85-0
106-44-5
1689-84-5
87-65-0
142-62-1
58-90-2
necessary, and concentrated. Extracts are
concentrated to one mL if GPC is not
performed, and to 0.5 mL if GPC is
performed. An internal standard is added
to the extract, and a one uL aliquot of
the extract is injected into the gas
chromatogrnph (GO. The compounds are
separated by GC and detected by a mass
spectrometer
-------
compounds listed in Tables 1 and 2. and
for other compounds for which . standards
and labeled analogs are available, the
GCMS system is calibrated and the compound
concentration is determined using an
isotope dilution technique. (2) For
compounds listed in Tables 1 and 2, and
for other compounds for which authentic
standards but no labeled compounds are
available, the GCMS system is calibrated
and the compound concentration is
determined using an internal standard
Table 5 '
GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS
EGD
No.
d?
164
930
261
361
585
580
603
703
917
598
610
710
916
577
589
582
562
922
557
613
713
265
365
218
318
617
717
226
326
227
327
225
325
935
564
242
342
571
263
363
555
212
312
937
919
Retention time
Compound
2,2'-difluorobiphenyl (int std)
pyridine
N-nitrosodimethylamine-d, <5>
N-nitrosodimethylamine <§>
N.N-dimethylformamide
1 ,2:3,4-diepoxybutane
alpha picoline-d7
alpha picoline
N- ni trosomethylethylamine
methyl methanesulfonate
styrene-dg
styrene
N-nitrosodiethylamine
1,3-dichloro-2-propanol
ethyl methanesulfonate
dimethyl sulfone
benzenethiol
pentachloroethane
aniline
p-cymene-d14
p-cymene
phenol -ds
phenol
bis(2-chloroethyl) ether-d»
bis<2-chloroethyl) ether
. n-C10-d-2
n-CIO
1 ,3-dichlorobenzene-d4
,3-dichlorobenzene
,4-dichlorobenzene-d.
,4-dichlorobenzene
,2-dichlorobenzene-d.
,2-dichlorobenzene
thioacetamide
benzyl alcohol
bis(2-chloroisopropyl) ether-d._
bis(2-chloroisopropyl) ether
o-cresol
N-nitrosodi-n-propylamine-d., (5)
N-nitrosodi-n-propylamine (5)
acetophenone
hexachloroethane- C
hexachloroethane
o-toluidine
N-nitrosomorpholine
Mean
(see)
1163
378
378
385
407
409
417
426
451
511
546
549
570
589
637
649
667
680
694
742
755
696
700
696
704
698
720
722
724
737
740
758
760
768
785
788
799
814
817
830
818
819
823
830
834
EGD
Ref
164
164
164
261
164
164
164
603
164
164
164
610
164
164
164
164
164
164
164
164
613
164
265
164
218
164
617
164
226
164
227
164
225
164
164
164
242
164
164
263
164
164
212
164
164
Relative (2)
1.000 - 1.000
0.325
0.286 - 0.364
1.006 - 1.028
0.350
0.352
0.326 - 0.393
1.006 - 1.028
0.338
0.439
0.450 - 0.488
1.002 - 1.009
0.490
0.506
0.548
0.558
0.574
0.585
0.597
0.624 - 0.652
1.008 - 1.023
0.584 - 0.613
0.995 - 1.010
0.584 • 0.607
1.007 - 1.016
0.585 - 0.615
1.022 - 1.038
0.605 - 0.636
0.998 - 1.008
0.601 - 0.666
0.997 • 1.009
0.632 - 0.667
0.995 - 1.008
0.660
0.675
0.664 - 0.691
1.010 - 1.016
0.700
0.689 - 0.716
1.008 - 1.023
0.703
0.690 - 0.717
0.999 - 1.001
0.714
0.717
Mini-
mum
Level
(3)
10
50
50
50
50
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
20
20
10
10
Method Detection
Limit (45
low high
solids solids
16 27
1 W Ctf
25 87
&.? Of
149* 17
Iff I 1
426* 912*
2501* 757*
32 22
299* 1188*
46 26
•tw CO
35 20
63 16
W«J IO
24 39
46 47
58 55
33
-------
Table 5 (continued)
CAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABUE COMPOUNDS
EGO
Ho.
575
256
356
566
565
941
254
354
942
920
234
334
243
343
208
308
558
255
355
934
609
709
606
706
629
729
252
352
918
592
569
570
915
923
561
931
939
904
599
568
938
933
253
353
594
594
578
574
220
320
Retention time
1,2-dibrofno-3-chloropropsne
nitrobenzene- dg
nitrobenzene
3-brcfflochlorobenzene
2-bro»ochlorobenzene
tripropylene glycol methyl ether
itophorone-dg
isophorone
1,3,5-trithiane
H-nitrosopiperidine
2,4-dimethylphenol-d,
2,4-dimethylphenol
" bis(2-chloroethoxy) methane-d, (5)
bi>(2-chloroethoxy) methane (5)
1 ^^-trichlorobenzene-dg
1,2,4-trichlorobenzene
o-anisidine
naphthalene-dg
naphthalene
thianapthene
alpha- terpineol-dj
alpha-terpineol
n~C]2-dy,
n-012
1,2,3-trichlorobenzene-d, (5)
1,2,3-trichlorobenzene (5)
hexachlorobutadiene- C^
hexachlorobutadiene
H-nStrosomethytphenylamine
hexach loropropene
4-chloroaniline
3- ch I oroni trobenzene
H-nitrosodi-n-butylaraine
pentwnethylbenzene
1,3-benzenediol
safrole
2,4,5-trimethylaniline
2-methylnaphthalene
2-methylbenzothiazole
5-chloro-o-toluidine
1 ,2,3-trimethoxybenzene
1,2,4,5-tetrachlorobenzene
hexachlorocyclopentadiene- c^
hexach lorocyc I opentadi ene
isosafrole (cis or trans)
isosafrole (cis or trans)
2,3-dichloroaniline
2,4-diaminotoluene
2-chloronaphthalene-d^
2-chloronaphthalene
Mean
(see)
839
845
849
854
880
881
881
889
889
895
921
924
933
93(9
955
958
962
963
967
971
973
975
953
981
1000
' 1003
1005
1006
1006
1013
1016
1018
1063
1083
1088
1090
1091
1098
1099
1101
1128
1141
1147
1142
1147
1190
1160
1187
1185
1200
EGO
Ref
164
164
256
164
164
164
164
254
164
164
164
234
164
243
164
208
164
164
255
164
164
609
164
606
164
629
164
252
164
164
164
164
164
164
164
164
164
164
164
164
164
164
164
253
164
164
164
164
164
220
Mini-
nun
Level
Relative f21 (UO/mL)
0.721
0.706 -
1.002 -
0.734
0.757
0.758
0.747 •
0.999 •
0.764
0.770
0.781 -
0.999 -
0.792 •
1.000 •
0.813 -
1.000 -
0.827
0.819 -
1.001 -
0.835
0.829 -
0.998 -
0.730 -
0.986 -
0.852 •
1.000 -
0.856 -
0.999 •
0.865
0.871
0.874
0.875
0.914
0.931
0.936
0.937
0.938
0.944
0.945
0.947
0.970
0.981
0.976 •
0.999 •
0.986
1.023
0.997
1.021
1.014 -
0.997 •
0.727
1.007
0.767
1.017
0.803
1.003
0.807
1.013
0.830
1.005
0.836
1.006
0.844
1.008
0.908
1.051
0.868
1.005
0.871
1.002
0.986
1.001
1.024
1.007
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
Method
Limit (
low
solids
(ua/kfl)
39
8
26
26
49
62
nd
860*
260*
46
nd
80
Detection
4)
high
solids
28
5
13
23
24
42
nd
3885*
164*
22
nd
59
34
-------
Table 5 (continued)
GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS
EGO
No.
0>
518
612
712
608
708
579
911
908'
595
277
377
593
587
576
271
371
573
236
336
912
201
301
605
705
921
909
235
335
602
702
590
280
380
240
340
270
370
906
567
910
913
619
719
237
337
607
707
262
362
241
341
Retention time
Comoound
n-C14
biphenyl-d1Q
biphenyl
diphenyl ether-d,.-
diphenyl ether
2,3-di ch loroni trobenzene
2-nitroaniline
1 ,4-naphthoquinone
longifolene
acenaphthylene-cL
acenaphthytene
2- isopropytnaphthalene
1,4-dini trobenzene
2.6-dichloro-4-nitroaniline
dimethyl phthalate-d.
dimethyl phthalate
2,6-di - t-butyl -p-benzoquinone
2,6-dimtrotoluene-cU
2,6-dinitrotoluene
3-nitroaniline
acenaphthene-d,g
acenaphthene
dibenzofuran-dg
dibenzofuran
pentach I or obenzene
alpha-naphthylamine
• 2,4-dinttrotoluene-d,
2,4-dinitrotoluene
b*ta-naphthylamine-d7
beta-naphthylamine
ethylenethiourea
fluorene-d.Q
fluorene
4-chlorophenyl phenyl ether-d~
4-chlorophenyl phenyl ether
diethyl phthalate-d.
diethyl phthalate
2- (methyl thio)benzothiazole
4-chloro-2-nitroaniline
5-nitro-o-toluidine
4-nitroaniline
n-Cte-d,,
n-C16
1 ,2-diphenylhydrazine-J)
1,2-diphenylhydrazine (6)
diphenylamine-d10
diphenylamine
N-nitrosodiphenylamine-dx
N-nitrosodiphenylamine (7)
4-bromophenyl phenyl ether-dg (5)
4-bromophenyl phenyl ether (5)
Mean
-------
Table 5 (continued)
CAS CHJIOHATOCRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS
EGO
Ho.
(1)
925
903
209
309
556
929
281
520
381
278
378
604
704
588
914
927
628
728
621
721
907
902
905
268
368
928
586
597
926
239
339
572
936
284
384
205
305
522
559
559
583
563
623
723
932
267
367
276
376
901
272
Retention time
phtnacatin
1-Methylfluortne ._
hexaehlorobtnzene- Cg
hexach lorobtnzene
4-a*inobiph«myl
pronamide
phtnanthrena-d.0
n-c18
phtnanthrtne
anthractne*d«n
• 10
anthracene
dfbtnzothfophtne-dg
dibenzothiophtne
dJphenylditulfide
4-nitrobiphtnyl
1 -phtny Inaphthalene
carbazole-dg (5)
carbazole (5)
n*C20*d
n-C20 . '
1,5-naphthaltntdtantne
4,5-Methyttntphenanthrene
1 -Mthylphtnanthrene
dt-n-butyl phthalate-d.
df-n-butyl ph thai ate
2-phenylnaphthalene
3,6-dfMthylphtnanthrene
•athapyri lene
phenothiazina
fluoranthene-djQ
fluoranthtnt
crotoxypho*
thtoxanthone
pyrtne-d.n
pyrent
btnzfdtna-d.
benzidine
n-C22
araaiite
aranite
p-diMthylaatnoazobenzene
2,3* btnzof luorene
n-C24-d,.0
n-C24
squaltne
butylbenzyl phthalate-d, (5)
butylbtnzyl phthalate (5)
chryttnt-d
chrystne
4,4 '-Mthyltntbi s<2-ch loroztni I ine)
btnzo(a)anthracene-dj2
Mean
1512
1514
1521
1522
1551
1578
1578
1580
1583
1588
1592
1559
1564
1623
1639
1643
1645
1650
1655
1677
1676
1690
1697
1719
1723
1733
1763
1781
1796
1813
1817
1822
1836
1844
1852
1854
1853
1889
1901
1916
1922
1932
1997
2025
2039
2058
2060
2081
2083
2083
2082
EGO
Ref
164
164
164
209
164
164
164
164
281
164
278
164
604
164
164
164
164
628
164
621
164
164
164
164
268
164
164
164
164
164
239
164
164
164
284
164
205
164
164
164
164
164
164
612
164
164
267
164
276
164
164
Relative (21
1.300
1.302
1.288 •
0.999 -
1.334
1.357
1.334 -
1.359
1.000 -
1.342 -
0.998 •
1.314 •
1.000 •
1.396
1.409
1.413
1.388 *
1.000 *
1.184 -
1.010 •
1.441
1.453
1.459
1.446 •
1.000 *
1.490
1.516
1.531
1.544
1.522 -
1.000 •
1.567
1.579
1.523 •
1.001 •
1.549 •
1.000 •
1.624
1.635
1.647
1.653
1.661
1.671 -
1.012 •
1.753
1.715 •
1.000 •
1.743 •
1.000 -
1.791
1.735 -
1.327
1.001
1.380
.005
.388
.006
.361
.006
1.439
1.006
1.662
1.021
1.510
1.003
1.596
1.004
1.644
1.003
1.632
1.002
.764
.015
.824
.002
.837
.004
1.846
Mini •
mum
Level
(3)
fuq/mL)
10
10
10
10
10
10
10
10
10
20
20
10
10
10
10
10
10
10,
10
50
50
10
10
10
10
10
10
10
10
Method Detection
Limit <4>
low high
solids solids
(uq/kq) (us/kg)
51 48
134* 844*
42 22
52 21
72 71
47 24
83 229*
64 80
54 22
40 48
nd nd
432* 447*
..
60 65
51 48
36
-------
Table 5 (continued)
GAS CHROMATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR BASE/NEUTRAL EXTRACTABLE COMPOUNDS
Mini-
Method Detection
i*uts
NO.
0)
372
581
228
328
940
560
266
366
CO/
524
591
269
369
525
584
274
374
275
375
924
273
373
626
726
596
900
083
282
382
279
379
Retention time
Comoound
benzo(a)anthracene
3,3' -dimethoxybenzidine
3,3'-dichlorobenzidine-d,
3,3« -dichlorobenzidine
triphenylene
benzanthrone
bis(2-ethylhexyl) phthalate-d.
bis(2-ethylhexyl) phthalate
n-C26
ethynylestradiol 3-methyl ether
di-n-octyl phthalate-d,
di-n-octyl phthalate
n-C28
7, 12-dimethylbenz(a)anthracene
benzo(b)fluoranthene-d12
benzo(b)fluoranthene
benzo(k)fluoranthene-d12
benzo( k) f I uoranthene
perylene
benzo(a)pyrene-d12
benzo(a)pyrene
n-C30-dfi2
n-C30
malachite green
3-methylcholanthrene
indenod ,2,3-cd)pyrene
dibenzo(a,h)anthracene-d,, (5)
dibenzo(a,h)anthracene (5)
benzo(ghi )perylene-d1 .
benzo(ghi)perylene
Mean
(see)
2090
2090
2088
2086
2088
2106
2123
2124
2147
2209
2239
2240
2272
2284
2281
2293
2287
2293
2349
2351
2350
2384
2429
2382
2439
2650
2649
2660
2741
2750
EGD
Ref
272
164
164
228
164
164
164
266
164
164
164
269
164
164
164
274
164
275
164
164
273
164
626
164
164
164
164
282
164
279
Relativ
0.999 -
1.797
1.744 •
1.000 -
1.795
1.811
1.771 •
1.000 -
1.846
1.899
1.867 -
1.000 -
1.954
1.964
1.902 -
1.000 -
1.906 -
1.000 •
2.020
1.954 -
1.000 -
1.972 •
1.011 -
2.048
2.097
2.279
2.107 -
1.000 -
2.187 -
1.001 •
e (2)
1.007
1.848
1.001
1.880
1.002
1.982
1.002
2.025
1.005
2.033
1.005
2.088
1.004
2.127
1.028
2.445
1.007
2.524
1.006
Level
10
50
50
10
10
10
10
10
10
10
10
10
10
10
10
10
10
20
20
20
20
20
low
solids
61
62
553*
609*
W7
72
492*
54
w*f
O5
,
52
252*
67
49
*»y
44
high
solids
47
*tl
111
III
1310*
RRA*
OOw
62
1810*
20
15
1 J
658*
263*
nd
method* r*far*n<-» ~n**^~*'\^-~"«*' ''•*?.'•?' "V'Tvi?"'" " P°llulont quaniiTiea oy tne internal standard
ct««2r^ tltC^f "foero beginning with 2 or 6 indicate a labeled compound quantified by the internal
dilution. reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope
(2) Single values in this column are based on single laboratory data.
This is a minimum level at uh?ch th* »MI«*JM. sy«tem^shaU give recognizable mass spectra (background
(4)
-------
Table 6
CAS CHROHATOGRAPHIC RETENTION TIMES AND DETECTION LIMITS FOR ACID EXTRACTABLE COMPOUNDS
EGO
Ho.
<1>
164
224
324
947
944
257
357
231
331
943
946
222
322
221
321
631
731
530
259
359
258
358
948
260
360
945
264
364
Retention time
Compound
2,2'-difluorobiphenyl
2,4,5-trtchlorophenol
2,3,6-trtchlorophenol
2,4-dinitrophenol-di,
2,4-dinitrophenol
4-nitrophenol-d,
4-nitrophenol
2,3,4, 6-tetrachlorophcnol
2-methyl-4,6-dInitrophenol-d2
2-methyl-4,6-dinitrophenol
3,5-dibroiK>-4-hydroxybenzonitrile
pentachlorophtnol- Cfi
ptntach I or opheno I
Mean
1163
701
705
746
834
898
900
944
947
971
981
1086
1091
1162
1165
1167
1170
1195
1323
1325
1349
1354
1371
1433
• 1435
1481
1559
1561
EGD
Ref
164
164
224
164
164
164
257
164
231
164
164
164
222
164
221
164
631
164
164
259
164
258
164
164
260
164
164
264
Relative <2>
1.000 - 1.000
0.587 - 0.618
0.997 • 1.010
0.641
0.717
0.761 • 0.783
0.994 - 1.009
0.802 • 0.822
0.997 - 1.006
0.835
0.844
0.930 - 0.943
0.998 - 1.003
0.994 •
0.998 -
0.998 -
0.998 -
1.028
1.127 -
1.000 -
1.147 -
0.997 -
1.179
1.216 -
1.000 -
.005
.004
.009
.004
.149
.005
.175
.006
.249
.002
1.273
1.320 • 1.363
0.998 • 1.002
Mini-
mum
Level
(3)
(ua/mL)
10
10
10
20
20
10
10
10
10
10
10
10
10
10
50
50
50
50
20
20
50
50
Method Detection
Limit (4)
low
solids
(ua/ka)
18
39
24
41
46
32
58
565
287
385
51
high
solids
(us/kg)
10
44
116
62
111
55
37
642
11
83
207
(1) Reference numbers, beginning with 0, 1, 5, or 9 indicate a pollutant quantified by the internal standard
method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal
standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope
dilution.
(2) Single values in this column are based on single laboratory data.
(3) This is a minimum level at which the analytical system shall give recognizable mass spectra (background
corrected) and acceptable calibration points. The concentration in the aqueous or solid phase is
determined using the equations in section 14.
(4) Method detection limits determined in digested sludge (low solids) and in filter cake or compost (high
solids).
(5) Specification derived from" related compound.
Colirn: 30 +/• 2 m x 0.25 +/- 0.02 mm i.d. 94X methyl, 4X phenyl, 1X vinyl bonded phase fused silica capillary
Temperature program: 5 min at 30°C; 30 - 250°C or. until pentachlorophenol elutes
Cis velocity: 30 +/- 5 cm/sec at 30°C
38
-------
technique. (3) For compounds listed in
Tables 3 and 4, and for other compounds
for which standards are not available,
compound concentrations are determined
using known response factors. (4) For
compounds for which neither standards nor
known response factors are available,
compound concentration is determined using
the sum of the EICP areas relative to the
sum of the EICP areas of the internal
standard.
2.4 The quality of the analysis is assured
through reproducible calibration and
testing of the extraction and GCMS
systems.
3 CONTAMINATION AND INTERFERENCES
3.1 Solvents, reagents, glassware, and other
sample processing hardware may yield
artifacts and/or elevated baselines
causing misinterpretation of chromatograms
and spectra. All materials used in the
analysis shall be demonstrated to be free
from interferences under the conditions of
analysis by running method blanks
initially and with each sample lot
(samples started through the extraction
process on a given 8 hr shift, to a
maximum of 20). Specific selection of
reagents and purification of solvents by
distillation in all-glass systems may be
required. Glassware and, where possible,
reagents are cleaned by solvent rinse and
baking at 450°C for one hour minimum.
3.2 Interferences coextracted from samples
will vary considerably from source to
source, depending on the diversity of the
site being sampled.
4 SAFETY
4.1 The toxicity or careinogenicity of each
compound or reagent used in this method
has not been precisely determined;
however, each chemical compound Should be
treated as a potential health hazard.
Exposure to these compounds should be
reduced to the lowest possible level. The
laboratory is responsible for maintaining
a current awareness file of OSHA
regulations regarding the safe handling of
the chemicals specified in this method. A
reference file of data handling sheets
should also be made available to all
personnel involved in these analyses.
Additional information on laboratory
safety can be found in References 3-5.
4.2 The following compounds covered by this
method have been tentatively-classified as
known or suspected human or mammalian
carcinogens: benzo(a)anthracene, 3,3'-
dichlorobenzidine, dibenzo(a,h)anthracene,
benzo(a)pyrene, N-nitrosodimethylamine,
and beta-naphthylamine. Primary standards
of these compounds shall be prepared in a
hood, and a NIOSH/MESA approved toxic gas
respirator should be worn when high
concentrations are handled.
5 APPARATUS AND MATERIALS
5.1 Sampling equipment for discrete or
composite sampling.
5.,1.1 Sample Bottles and Caps
5.1.1.1 Liquid Samples (waters, sludges and
similar materials that contain less than
five percent solids)--Sample bottle, amber
glass, 1.1 liters minimum, with screw cap.
5.1.1.2 Solid samples (soils, sediments, sludges,
filter cake, compost, and similar
materials that contain more than five
percent solids)--Sample bottle, wide
mouth, amber glass, 500 ml minimum.
5.1.1.3 If amber bottles are not available,
samples shall be protected from light.
5.1.1.4 Bottle caps—threaded to fit sample
bottles. Caps shall be lined with Teflon.
5.1.1.5 Cleaning
5.1.1.5.1 Bottles are detergent water washed, then
solvent rinsed or baked at 450 °C for one
hour minimum before use.
5.1.1.5.2 Cap liners are washed with detergent and
water, rinsed with reagent water (see
Section 6.5.1) and then solvent, and then
baked for at least one hour at
approximately 200 °C.
5.1.2 Compositing equipment--automatic or manual
compositing system incorporating glass
containers cleaned per bottle cleaning
procedure above. Sample containers are
kept at 0 - 4 °C during sampling. Only
glass or Teflon tubing shall be used. If
the sampler uses a peristaltic pump, a
39
-------
minimum length of compressible silicone
rubber tubing may be used only in the
ptnp. Before use, the tubing shall be
thoroughly rinsed with metHanoi, followed
by repeated rinsings with reagent water
(Section 6.5.1) to minimize sample
contamination. An integrating flow meter
is used to collect proportional composite
samples.
5.2 Equipment for determining percent moisture
5.2.1 Oven, capable of Maintaining a temperature
of 110 ± 5 -C.
5.2.2 Dessicator
5.3 Sonic disruptoi—375 watt with pulsing
capability and 3/4 in. disrupter horn
(Ultrasonics, Inc, Model 375C, or
equivalent).
5.4 Extraction apparatus
5.4.1 Continuous liquid-liquid extractor—Teflon
or glass connecting joints and stopcocks
without lubrication, 1.5 - 2 liter
capacity (Hershberg-Uolf Extractor, Ace
Glass 6841-10, or equivalent).
5.4.2 Beakers
5.4.2.1 1.5 - 2 liter, borosilicate glass beakers
calibrated to one liter
5.4.2.2 400 - 500 mL borosilicate glass beakers
5.4.2.3 Spatulas—stainless steel
5.4.3 Filtration apparatus
5.4.3.1 Glass funnel—125 - 250 mL
5.4.3.2 Filter paper for above (Whatman 41, or
equivalent)
5.5 Drying colum--15 to 20 ran i.d. Pyrex
chromatographic column equipped with
coarse glass frit or glass wool plug.
5.6 Concentration apparatus
5.6.1 Concentrator tube--Kuderna-Danish (K-D) 10
mL, graduated (Kontes K-570050-1025, or
equivalent) with calibration verified.
Ground glass stopper (size 19/22 joint) is
used to prevent evaporation of extracts.
5.6.2 Evaporation flask--Kuderna-Danish (K-D)
500 mL (Kontes K-570001-0500, or
equivalent), attached to concentrator tube
with springs (Kontes K-662750-0012).
5.6.3 Snyder column--Kuderna-Danish (K-D) three
ball macro (Kontes K-503000-0232, or
equivalent).
5.6.4 Snyder column—Kuderna-Danish (K-D) two
ball micro (Kontes K-469002-0219, or
equivalent).
5.6.5 Boiling chips—approx 10/40 mesh,
extracted with methylene chloride and
baked at 450 °C for one hour minimum.
5.6.6 Nitrogen evaporation device—equipped with
a water bath that can be maintained at 35
'- 40 "C. The N-Evap by Organomation
Associates, Inc., South Berlin, MA (or
equivalent) is suitable.
5.7 Water bath—heated, with concentric ring
cover, capable of temperature control (± 2
°C), installed in a fume hood.
5.8 Sample vials—amber glass, 2 - 5 ml with
Teflon-lined screw cap.
5.9 Balances
5.9.1 Analytical--capable of weighing 0.1 mg.
5.9.2 Top loading—capable of weighing 10 mg.
5.10 Automated gel permeation chromatograph
(Analytical Biochemical Labs, Inc.,
Columbia, MO, Model GPC Autoprep 1002, or
equivalent)
5.10.1 Column--600 - 700 mm x 25 mm i.d., packed
with 70 g of SX-3 Bio-beads (Bio-Rad
Laboratories, Richmond, CA)
5.10.2 UV detectors -- 254-mu, preparative or
semi-prep flow cell:
5.10.2.1 Schmadzu, 5 mm path length
5.10.2.2 Beckman-Altex 152U, 8 uL micro-prep flow
cell, 2 mm path
5.10.2.3 Pharmacia UV-1, 3 mm flow cell
5.10.2.4 LDC Milton-Roy UV-3, monitor #1203
40
-------
5.11
5.11.1
5.12
5.13
Gas chromatograph--shall have splitless or
on-column injection port for capillary
column, temperature program with 30 "C
hold, and shall meet all of the
performance specifications in Section 12.
Column--30 ±5 m x 0.25 ± 0.02 ran i.d. 5X
phenyl, 94* methyl, 1% vinyl silicons
bonded phase fused silica capillary column
(J & U DB-5, or equivalent).
Mass spectrometer—70 eV electron impact
ionization, shall repetitively scan from
35 to 450 amu in 0.95 - 1.00 second, and
shall produce a unit resolution (valleys
between ai/z 441-442 less than 10 percent
of the height of the 441 peak), background
corrected mass spectrum from 50 ng
decafluorotriphenylphosphine (DFTPP) in-
troduced through the GC inlet. The
spectrum shall meet the mass-intensity
criteria in Table 7 (Reference 6). The
mass spectrometer shall be interfaced to
the GC such that the end of the capillary
column terminates within one centimeter of
the ion source but does not intercept the
electron or ion beams. All portions of
the column which connect the GC to the ion
source shall remain at or above the column
temperature during analysis to preclude
condensation of less volatile compounds.
Table 7
DFTPP MASS-INTENSITY SPECIFICATIONS*
Mass
Intensity reotn'red
51
68
69
70
127
197
198
199
275
441
442
443
8-82 percent of m/z 198
less than 2 percent of m/z 69
11-91 percent of m/z 198
less than 2 percent of m/z 69
32 - 59 percent of m/z 198
less than 1. percent of m/z 198
base peak, 100 percent abundance
4-9 percent of m/z 198
11-30 percent of m/z 198
44-110 percent of m/z 443
30-86 percent of m/z 198
14 - 24 percent of m/z 442
*Reference 6
Data system—shall collect and record MS
data, store mass- intensity data in
spectral libraries, process GCMS data,
generate reports, and shall compute and
record response factors.
5.13.1 Data acquisition—mass spectra shall be
collected continuously throughout the
analysis and stored on a mass storage
device.
5.13.2 Mass spectral libraries—user created
libraries containing mass spectra obtained
from analysis of authentic standards shall
be employed to reverse search GCMS runs
for the compounds of interest (Section
7.2).
5.13.3 Data processing—the data system shall be
used to search, locate, identify, and
quantify the compounds of interest in each
GCMS analysis. Software routines shall be
employed to compute retention times and
peak areas. Displays of spectra, mass
chromatograms, and library comparisons are
required to verify results.
5.13.4 Response factors and multipoint
calibrations—the data system shall be
used to record and maintain lists of
response factors (response ratios for
isotope dilution) and multi-point
calibration curves (Section 7).
Computations of relative standard
deviation (coefficient of variation) are
used for testing calibration linearity.
Statistics on initial (Section 8.2) and
on-going (Section 12.7) performance shall
be computed and maintained.
6 REAGENTS AND STANDARDS
6.1 Reagents for adjusting sample pH
6.1.1 Sodium hydroxide--reagent grade, 6N in
reagent water.
6.1.2 Sulfuric acid—reagent grade, 6N in
reagent water.
6.2 Sodium sulfate--reagent grade, granular
anhydrous, rinsed with methylene chloride
(20 mL/g), baked at 450 °C for one hour
minimum, cooled in a dessicator, and
stored in a pre-cleaned glass bottle with
screw cap which prevents moisture from
entering.
6.3 Methylene chloride—distilled in glass
(Burdick and Jackson, or equivalent).
6.4 GPC calibration solution — containing 300
mg/mL corn oil, 15 mg/mL bis(2-ethylhexyl)
41
-------
phthalate, 1.4 mg/mL pentachlorophenol,
0.1 mg/mL perylene, and 0.5 mg/mL sulfur.
6.5 Reference matrices
6.5.1 Reagent water—water in which the
compounds of interest and interfering
compounds are not detected by this method.
6.5.2 High solids reference matrix—playground
sand or similar material in which the
compounds of interest and interfering
cotnpounds are not detected by this method.
6.6 Standard solutions—purchased as solutions
or mixtures with certification to their
purity, concentration, and authenticity,
or prepared from materials of known purity
and composition. If compound purity is 96
percent or greater, the weight may be used
without correction to compute the
concentration of the standard. When not
being used, standards are stored in the
dark at -20 to -10 °C in screw-capped
vials with Teflon-lined lids. A mark is
placed on the vial at the level of the
solution so that solvent evaporation loss
can be detected. The vials are brought to
room temperature prior to use. Any
precipitate is redissolved and solvent is
added if solvent loss has occurred.
6.7 Preparation of stock solutions—prepare in
methylene chloride, benzene, p-dioxane, or
a mixture of these solvents per the steps
below. Observe the safety precautions in
Section 4. The large number of labeled
and unlabeled acid and base/neutral
compounds used for combined calibration
(Section 7) and calibration verification
(12.5) require high concentrations (approx
40 mg/mL) when individual stock solutions
are prepared, so that dilutions of
mixtures will permit calibration with all
compounds in a single set of solutions.
The working range for most compounds is
10-200 ug/mL. Compounds with a reduced US
response may be prepared at higher
concentrations.
6.7.1 Dissolve an appropriate amount of assayed
reference material in a suitable solvent.
For example, weigh 400 mg naphthalene in a
10 mL ground glass stoppered volumetric
flask and fill to the mark with benzene.
After the naphthalene is completely
dissolved, transfer the solution to a 15
mL vial with Teflon-lined cap.
6.7.2 Stock standard solutions should be checked
for signs of degradation prior to the
preparation of calibration or performance
test standards. Quality control check
samples that can be used to determine the
accuracy of calibration standards are
available from the US Environmental
Protection Agency, Environmental Monitor-
ing and Support Laboratory, Cincinnati,
Ohio 45268.
6.7.3 Stock standard solutions shall be replaced
after six months, or sooner if comparison
with quality control check standards
indicates a change in concentration.
6.8 Labeled compound spiking solution—from
stock standard solutions prepared as
above, or from mixtures, prepare the
spiking solution at a concentration of 200
ug/mL, or at a concentration appropriate
to the MS response of each compound.
6.9 Secondary standard—using stock solutions
(Section 6.7), prepare a secondary
standard containing all of the compounds
in Tables 1 and 2 at a concentration of
400 ug/mL, or higher concentration
appropriate to the MS response of the
compound.
6.10 Internal standard solution—prepare 2,2'-
difluorobiphenyl (DFB) at a concentration
of 10 mg/mL in benzene.
6.11 DFTPP solution—prepare at 50 ug/mL in
acetone.
6.12 Solutions for obtaining authentic mass
spectra (Section 7.2)--prepare mixtures of
compounds at concentrations which will
assure authentic spectra are obtained for
storage in libraries.
6.13 Calibration solutions--combine 5 aliquots
of 0.5 mL each of the solution in Section
6.8 with 25, 50, 125, 250, and 500 uL of
the solution in Section 6.9 and bring to
1.00 mL total volume each. This will
produce calibration solutions of nominal
10, 20, 50, 100 and 200 ug/mL of the
pollutants and a constant nominal 100
ug/mL of the labeled compounds. Spike
each solution with 10 uL of the internal
standard solution (Section 6.10). These
solutions permit the relative response
(labeled to unlabeled) to be measured as a
function of concentration (Section 7.4).
42
-------
6.14 Precision and recovery standard—used for
determination of initial (Section 8.2) and
on-going (Section 12.7) precision and
recovery. This solution shall contain the
pollutants and labeled compounds at a
nominal concentration of 100 ug/mL.
6.15 Stability of solutions—al I standard
solutions (Sections 6.8 - 6.14) shall be
analyzed within 48 hours of preparation
and on a monthly basis thereafter for
signs of degradation. Standards will
remain acceptable if the peak area at the
quantisation mass relative to the OFB
internal standard remains within ± 15
percent of the area obtained in the
initial analysis of the standard.
7 CALIBRATION
7.1 Assemble the GCNS and establish the
operating conditions in Table 5. Analyze
standards per the procedure in Section 11
to demonstrate that the analytical system
meets the minimum levels in Tables 5 and
6, and the mass-intensity criteria in
Table 7 for 50 ng OFTPP.
7.2 Mass spectral libraries—detection and
identification of compounds of interest
are dependent upon spectra stored in user
created libraries.
7.2.1 Obtain a mass spectrum of each pollutant,
labeled compound, and the internal
standard by analyzing an authentic
standard either singly or as part of a
mixture in which there is no interference
between closely eluted components.
.Examine the spectrum to determine that
only a single compound is present.
Fragments not attributable to the compound
under study indicate the presence of an
interfering compound.
7.2.2 Adjust the analytical conditions and scan
rate (for this test only) to produce an
undistorted spectrum at the GC peak
maximum. An undistorted spectrum will
usually be obtained if five complete
spectra are collected across the upper
half of the GC peak. Software algorithms
designed to "enhance" the spectrum may
eliminate distortion, but may also
eliminate authentic masses or introduce
other distortion.
7.2.3 The authentic reference spectrum is
obtained under DFTPP tuning conditions
(Section 7.1 and Table 7) to normalize it
to spectra from other instruments.
7.2.4 The spectrum is edited by saving the 5
most intense mass spectral peaks and all
other mass spectral peaks greater than 10
percent of the base peak. The spectrum
may be further edited to remove common
interfering masses. If 5 mass spectral
peaks cannot be obtained under the scan
conditions given in Section 5.12, the mass
spectrometer may be scanned to an m/z
lower than 35 to gain additional spectral
information. The spectrum obtained is
stored for reverse search and for compound
confirmation.
7.2.5 For the compounds in Tables 3 and 4 and
^ for other compounds for which the mass
spectra, quantisation m/z's, and retention
times are known but the instrument is not
to be calibrated, add the retention time
and reference compound (Tables 5 and 6);
the response factor and the quantitation
m/z (Tables 8 and 9); and spectrum
(Appendix A) to the reverse search
library. Edit the spectrum per Section
7.2.4, if necessary.
7.3 Analytical range--demonstrate that 20 ng
anthracene or phenanthrene produces an
area at m/z 178 approx one-tenth that
required to exceed the linear range of the
system. The exact value must be
determined by experience for each
instrument. It is used to match the
calibration range of the instrument to the
analytical range and detection limits
required, and to diagnose instrument
sensitivity problems (Section 15.3). The
20 ug/mL calibration standard (Section
6.13) can be used to demonstrate this
performance.
7.3.1 Polar compound detection--demonstrate that
unlabeled pentachlorophenol and benzidine
are detectable at the 50 ug/mL level (per
all criteria in Section 13). The 50 ug/mL
calibration standard (Section 6.13) can be
used to demonstrate this performance.
7.4 Calibration with isotope dilution—isotope
dilution is used when 1) labeled compounds
are available, 2) interferences do not
preclude its use, and 3) the quantitat ion
m/z (Tables 8 and 9) extracted ion current
43
-------
Table 8
CHARACTERISTIC H/Z'S AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS
Response
Labeled Primary Factor
i2L
Response
acenaphthen*
acenaphthylene
acetophenonc
4-arainob!phenyl
ant line
o-anisfdine
anthracene
araraite
benzanthrone
1,3-benzenediol
benzenethiol
bcnzidinc
benzo(a)anthracena
benzo(b)fluoranthene
benzo(k)fluoranthene
benzo(a)pyren«
benzoCgM )perylene
2,3-benzofluorcne
benzole acid
benzyl alcohol
biphenyl
bi«(2-chloro«thyl) ether
bi»(2-chloroethoxy)n»ethane
bl»(2-chloroisopropyl) ether
bi*(2-ethylhexyl) phthalate
2-broDochlorobenzene
3-bfomochlorobenzene
4-bromophenyl phenyl ether
butyl benzyl phthalate
n-C10
n-C12
n-Cl4
n-M6
n-Cl8
n-C20
n-C22
n-C24
n-C26
n-C28
n-C30
carbazole
4-chloro-2-nitroani line
5-chloro-o-toluidine
4-chloroanUine
2-chloronaphthalene
3- ch loroni trobenzene
d10
*t
d10
d8
d12
d12
d12
d12
d12
d10
d8
d6
d12
d4
d5
d4
"22
d26
d,.
d42
dso
d62
d8
d7
154/164
152/160
105
169
93
108
178/188
185
230
110
110
184/192
228/240
252/264
252/264
252/264
276/288
216
105
79
154/164
93/101
93/99
121/131
149/153
111
192
248/253
149/153
57/82
57/66
57
57/66
57
57/66
57
57/66
57
57
57/66
167/175
172
106
127
162/169
157
0.79
0.81
1.04
0.43
0.19
0.15
0.78
0.18
.1
0.35
0.16
0.47
0.33
0.40
0.20
0.50
0.73
0.18
Labeled
Comnound Analog
4-chlorophenyl phenyl ether
3-chloropropionitri le
chrysene
o-cresol
crotoxyphos
p-cymene
2,6-di-tert-butyl-p-
benzoquinone
di-n- butyl phthalate
2,4-diaminotoluene
dibenzo
0.42
0.59
0.017
0.078
0.059
0.22
0.019
0.68
0.47
0.11
0.27
0.19
0.40
0.23
0.58
0.51
0.72
0.24
0.25
0.28
0.22
44
-------
Table 8 (cont.)
CHARACTERISTIC M/Z'S AND RESPONSE FACTORS OF BASE/NEUTRAL EXTRACTABLE COMPOUNDS
Response
Labeled Primary Factor
Compound Ana loo
ethynylestradiol 3 -me thy I
ether
fluoranthene d1Q
fluorene d1Q
hexach lorobenzene C,
hexach I orobutadi ene C,
hexach loroethane C,
hexachlorocyclopentadiene C,
hexach loropropene
indenod ,2,3-cd)pyrene
isophorone d_
2- isopropylnaphthalene
isosafrole
longifolene
malachite green
methapyrilene
methyl methanesulfonate
2-methylbenzothiazole
3-methylcholanthrene
4,4l-methylenebis
(2-chloroaniline)
4,5-methylenephenanthrene
1 • me t hy I f I uor ene
2-methylnaphthalene
1 -methyl phenanthrene
2- (methyl thio)benzothiazole
naphthalene d.
1 ,5-naphthalenediamine
1 ,4-naphthoquinone
alpha-naphthylamine
beta-naphthylamine d_
5-nitro-o-toluidine
2-nitroaniline
3-nitroaniline
4-nitroaniline
nitrobenzene d.
4-nitrobiphenyl
N-nitrosodi-n-butylamine
N-nitrosodi-n-propylamine d..
N-nitrosodiethylamine
N-nitrosodimethylamine d,
o
N-nitrosodiphenylamine (4) d.
N-nitrosomethylethylamine 88
N-nitrosomethylphenylamine 106
N-nitrosomorpholine 56
m/z (1>
227
202/212
166/176
284/292
225/231
201/204
237/241
213
276
82/88
170
162
161
330
97
80
149
268
231
190
180
1*2
192
181
128/136
158
158
143
143/150
152
138
138
138
123/128
199
84
70/78
102
74/80
169/175
0.33
0.024
0.49
(2)
0.28
0.23
0.32
0.33
0.14
0.43
0.20
0.59
0.59
0.21
0.44
0.37
0.99
0.65
0.42
0.085
0.021
0.89
0.31
0.39
0.27
0.11
0.35
0.47
0.45
Compound
Response
Labeled Primary Factor
Analog m/z (1) <2)
N-nitrosopiperidine
pentachlorobenzene
pentachloroethane
pent amethyIbenzene
perylene
phenacetin
phenanthrene
phenol
phenothiazine
1-phenylnaphthalene
2-phenylnaphthalene
alpha-picoline
pronamide
pyrene
pyridine
safrole
squalene
styrene
alpha-terpineol
1,2,4,5-tetrachlorobenzene
thiahaphthene
thioacetamide
thioxanthone
o-toluidine
1,2,3-trichlorobenzene
1,2,4-trichlorobenzene
1,2,3-trimethoxybenzene
2,4,5-trimethylaniline
triphenylene
tripropylene glycol methyl
ether
1,3,5-trithiane
"10
Is
"3
114
248
117
148
252
108
1Q 178/188
g 94/71
199
204
204
7 93/100
173
202/212
79
162
69
104/109
59/62
216
134
75
.212
106
180/183
180/183
168
120
228
59
138
0.41
0.25
0.20
0.42
0.30
0.38
0.15
0.48
0.73
0.31
0.68
0.45
0.042
0.43
1.52
0.28
0.23
1.04
0.48
0.28
1.32
0.092
0.15
(1) native/labeled
<2> referenced to 2,2'-difluorobiphenyl
(3) detected as azobenzene
<4) detected as diphenylamine
NOTE: Because the composition and purity of
commercially-supplied isotopically labeled standards
may vary, the primary m/z of the labeled analogs
given in this table should be used as guidance. The
appropriate m/z of the labeled analogs should be
determined prior to use for sample analysis. Devia-
tions from the m/z's listed here must be documented
by the laboratory and submitted with the data.
45
-------
Table 9
CHARACTERISTIC H/Z'S AND RESPONSE FACTORS OF ACID
EXTRACTABLE COMPOUNDS
Labeled
Confound Ana loo
benzoic acid
4-chloro-3-roethylphenol
2-chlorophenol
p-cresol
3,5-dibrowo-
4-hydroxybenzonitri le
2',4-dichlorophenol
2,6-dfchlorophenot
2,4-dinitrophenol
hexanoic acid
2-raethyl-4,6-dinitrophenol
2-nftrophenol
4-nitrophtnol
pentach lorophenol
2,3,4,6-tetrachlorophenol
2,3,6-trichlorophenol
2,4,5-trichlorophenol
2,4,6-trichlorophenol
"2
d4
*3
"3
"2
d4
13d*
"C6
*2
"2
"2
Primary
m/z (1)
105
107/109
128/132
108
277
162/167
162
184/187
60
198/200
65/109
65/109
266/272
232
196/200
196/200
196/200
Response
Factor
(2)
0.16
0.61
0.12
0.42
0.62
0.17
(1) native/labeled
(2) referenced to 2,2'-difluorobiphenyl
KOTE: Because the composition and purity of
cooroerciallysupplied isotopically labeled standards
m«y vary, the primary m/z of the labeled analogs
given In this table should be used as guidance. The
appropriate m/z of the labeled analogs should be
determined prior to use for sample analysis. Devia-
tions from the m/z's listed here must be documented
by the laboratory and submitted with the data.
10-
LU
I
fL
UJ
> 1.0
5
0.1-
T
T
-] 1 T
2 10 20 50 100 200
CONCENTRATION (ug/mL)
FIGURE 1 Relative Response Calibration Curve
for Phenol. The Dotted Lines Enclose a ± 1O Per-
cent Error Window.
a calibration curve for phenol using
phenol-d, us the isotopic diluent. Also
shown are the i 10 percent error limits
(dotted lines). Relative Response (RR) is
determined according to the procedures
described lac low. A minimum of five data
points are employed for calibration.
7.4.2 The relative response of a pollutant to
its labeled analog is determined from
isotope ratio values computed from
acquired data. Three isotope ratios are
used in this process:
R = the isotope ratio measured for the
pure pollutant.
7.4.1
profile (EICP) area for the compound is in
the calibration range. Alternate labeled
compounds and quantitation m/z's may be
used based on availability. If any of the
above conditions preclude isotope
dilution, the internal standard method
(Section 7.5) is used.
A calibration curve encompassing the
concentration range fs prepared for each
compound to be determined. The relative
response (pollutant to labeled) vs
concentration in standard solutions is
plotted or computed using a linear
regression. The example in Figure 1 shows
the isotope ratio measured for the
labeled compound.
R * the isotope ratio of an analytical
mixture of pollutant and labeled
compounds.
The m/z's are selected such that R > R .
If Rm is not between 2R and 0.5RX, the
method does not apply and the sample is
analyzed by the internal standard method.
7.4.3 Capillary columns usually separate the
pollutant-labeled pair, with the labeled
compound eluted first (Figure 2). For
this case,
46
-------
AREA AT
AREA AT
M,/Z
FIGURE 2 Extracted Ion Current Profiles for
Chromatographically Resolved Labeled (m,/z)
and Unlabeled (m,/z) Pairs.
(3A)
AREA = 46100
AREA = 4780
(3B)
AREA = 2650
AREA = 43600
AREA =48300
[area rn^/z (at RT-^M
V
[area n^/z (at
R = [area m./z (at RT-13
* tarea nig/z (at RT^J
as measured in the mixture of the
pollutant and labeled compounds (Figure
2), and RR a R .
m
7.4.4 Special precautions are taken when the
pollutant- labeled pair is not separated,
or when another labeled compound with
interfering spectral masses overlaps the
pollutant (a case which can. occur with
isomeric compounds). In this case, it is
necessary to determine the respective.
contributions of the pollutant and labeled
compounds to the respective EICP areas.
If the peaks are separated well enough to
permit the data system or operator to
remove the contributions of the compounds
to each other, the equations in Section
7.4.3 apply. This usually occurs when the
height of the valley between the two GC
peaks at the same m/z is less than 10
percent of the height of the shorter of
the two peaks. If significant GC and
spectral overlap occur, RR is computed
using the following equation:
RR = (R - R )(R + 1)
< - Rx'>
where R is measured as shown in Figure
3A, R is measured as shown in Figure 38,
and R is measured as shown in Figure 3C.
For the example,
46100
4780
9.644
<3C)
AREA = 49200
FIGURE 3 Extracted Ion Current Profiles for (3A)
Unlabeled Compound, (3B) Labeled Com-
pound, and (3C) Equal Mixture of Unlabeled
and Labeled Compounds.
7.4.5
7.4.6
2650
43600
0.06078
R = 49200 = 1.019
48300
RR = 1.115.
The data from these analyses are reported
to three significant figures (see Section
14.6). Therefore, in order to prevent
rounding errors from affecting the values
to be reported, all calculations performed
prior to the final determination of
concentrations should be carried out using.
at least four significant figures.
To calibrate the analytical system by
isotope dilution, analyze a 1.0 uL aliquot
of each of the calibration standards
(Section 6.13) using the procedure in
Section 11. Compute the RR at each
concentration.
Linearity-if the ratio of relative
response to concentration for any compound
is constant (less than 20 percent
coefficient of variation) over the 5 point
calibration range, an averaged relative
response/concentration ratio may be used
for that compound; otherwise, the complete
-------
calibration curve for that compound shall
b* used over the 5 point calibration
range.
7.5 Calibration by internal standard—used
when criteria for isotope dilution
(Section 7.4) cannot be met. The internal
standard to be used for both acid and
base/neutral analyses is 2,2'-difluorobi-
phenyl. The internal standard method is
also applied to determination of compounds
having no labeled analog, and to
measurement of labeled compounds for
intra*laboratory statistics (Sections 8.4
and 12.7.4).
7.5.1 Response factors—calibration requires the
determination of response factors (RF)
which are defined by the following
equation:
7.5.1.1
7.5.1.2
RF * (A^ x C,a).
(A,, X C8)
where
AS is the area of the characteristic mass
for the compound in the daily standard
*is ** the area of the characteristric
mass for the internal standard
C. is the concentration of the internal
standard (ug/mL)
C is the concentration of the compound in
the daily standard (ug/mL)
The response factor is determined for at
least five concentrations appropriate to
the response of each compound (Section
6.13); nominally, 10, 20, 50, 100, and 200
ug/mL. The amount of internal standard
added to each extract is the same (100
ug/mL) so that C. remains constant. The
RF is plotted vs concentration for each
compound in the standard (Cg) to produce a
calibration curve.
Linearity—if the response factor (RF) for
any compound is constant (less than 35
percent coefficient of variation) over the
5 point calibration range, an averaged
response factor may be used for that
compound; otherwise, the complete
calibration curve for that compound shall
be used over the 5 point range.
7.6 Combined calibration—by using calibration
solutions (Section 6.13) containing the
pollutants, labeled compounds, and the
internal standard, a single set of
analyses can be used to produce
calibration curves for the isotope
dilution and internal standard methods.
These curves are verified each shift
(Section 12.5) by analyzing the 100 ug/mL
calibration standard (Section 6.13).
Recalibration is required only if
calibration verification (Section 12.5)
criteria cannot be met.
8 QUALITY ASSURANCE/QUALITY CONTROL
8.1 Each laboratory that uses this method is
required to operate a formal quality
assurance program (Reference 7). The
minimum requirements of this program
consist of an initial demonstration of
laboratory capability, analysis of samples
spiked with labeled compounds to evaluate
and document data quality, and analysis of
standards and blanks as tests of continued
performance. Laboratory performance is
compared to established performance
criteria to determine if the results of
analyses meet the performance
characteristics of the method. If the
method is to be applied routinely to
samples containing high solids with very
little moisture (e.g., soils, filter cake,
compost), the high sol ids, reference matrix
(Section 6.S.2) is substituted for the
reagent water (6.5.1) in all performance
tests, and the high solids method (Section
10) is used for these tests.
8.1.1 The analyst shall make an initial
demonstration of the ability to generate
acceptable accuracy and precision with
this method,, This ability is established
as described! in Section 8.2.
8.1.2 The analyst is permitted to modify this
method to improve separations or lower the
costs of measurements, provided all
performance specifications are met. Each
time a modification is made to the method,
the analyst is required to repeat the
procedure in Section 8.2 to demonstrate
method performance.
8.1.3 Analyses of blanks are required to
demonstrate freedom from contamination.
The procedures and criteria for analysis
of a blank are described in Section 8.5.
48
-------
8.1.4 The laboratory shall spike all samples
with labeled compounds to monitor method
performance. This test is described in
Section 8.3. When results of these spikes
indicate atypical method performance for
samples, the samples are diluted to bring
method performance within acceptable
limits (Section 15).
8.1.5 The laboratory shall, on an on-going
basis, demonstrate through calibration
verification and the analysis of the
precision and recovery standard (Section
6.14) that the analysis system is in
control. These procedures are described
in Sections 12.1, 12.5, and 12.7.
8.1.6 The laboratory shall maintain records to
define the quality of data that is
generated. Development of accuracy
statements is described in Section 8.4.
present a substantial probability that one
or more will fail the acceptance criteria
when all compounds are analyzed. To
determine if the analytical system is out
of control, or if the failure can be
attributed to probability, proceed as
follows:
8.2.4 Using the results of the second set of
four analyses, compute s and X for only
those compounds which failed the test of
the first set of four analyses (Section
8.2.3). If these compounds now pass,
system performance is acceptable for all
compounds and analysis of blanks and
samples may begin. If, however, any of
the same compounds fail again, the
analysis system is not performing properly
for these compounds. In this event,
correct the problem and repeat the entire
test (Section 8.2.1).
8.2 Initial precision and accuracy--to
establish the ability to generate
acceptable precision and accuracy, the
analyst shall perform the following
operations:
8.2.1 For low solids (aqueous samples), extract,
concentrate, and analyze two sets of four
one-liter aliquots (8 aliquots total) of
the precision and recovery standard
(Section 6.14) according to the procedure
in Section 10. For high solids samples,
two sets of four 30 gram aliquots of the
high solids reference matrix are used.
8.2.2 Using results of the first set of four
analyses, compute the average recovery (X)
in ug/mL and the standard deviation of the
recovery (s) in ug/mL for each compound,
by isotope dilution for pollutants with a
labeled analog, and by internal standard
for labeled compounds and pollutants with
no labeled analog.
8.2.3 For each compound, compare s and X with
the corresponding limits for initial
precision and accuracy in Table 10. If s
and X for all compounds meet the
acceptance criteria, system performance is
acceptable and analysis of blanks and
samples may begin. If, however, any
individual s exceeds the precision limit
or any individual X falls outside the
range for accuracy, system performance is
unacceptable for that compound. NOTE: The
large number of compounds in Table 10
8.3 The laboratory shall spike all samples
with labeled compounds 'to assess method
performance on the sample matrix.
8.3.1 Analyze each sample according to the
method beginning in Section 10.
8.3.2 Compute the percent recovery (P) of the
labeled compounds using the internal
standard method (Section 7.5).
8.3.3 Compare the labeled compound recovery for
each compound with the corresponding
limits in Table 10. If the recovery of
any compound falls outside its warning
limit, method performance is unacceptable
for that compound in that sample.
Therefore, the sample is complex. Water
samples are diluted, and smaller amounts
of soils, sludges, and sediments are
reanalyzed per Section 15.
8.4 As part of the QA program for the
laboratory, method accuracy for samples
shall be assessed and records shall be
maintained. After the analysis of five
samples or a given matrix type (water,
soil, sludge, sediment) for which the
labeled compounds pass the tests in
Section 8.3, compute the average percent
recovery (P) and the standard deviation of
the percent recovery (s ) for the labeled
compounds only. Express the accuracy
assessment as a percent recovery interval
from P -2s to P + 2s for each matrix.
-------
Table 10
ACCEPTANCE CRITERIA FOR'PERFORMANCE TESTS
EGO
HO.
301
201
377
277
378
278
305
205
372
272
374
274
375
275
373
273
379
279
712
612
318
218
343
243
342
242
366
266
341
241
367
267
717
617
706
606
518
719
619
520
721
621
522
723
623
524
Labeled and
native compound
initial precision
and accuracy
{Sec 8.2.3) (ug/Li
Compound
acenaphthene
acenaphthene-d^Q
acenaphthylene
acenaphthylene-dg
anthracene
•nthracerwd10
benzidine
benzidine-dg
benzo(a)antnracene
benzo(a)anthracene-d12
benzo(b)fluoranthene
benzo(b)fluoranthene-d12
benzo(k)f luoranthen*
b*nzo(k)fluoranthene-d12
benzo(a)pvrene
b«nzo(a)pyrene-d^2
btnzo(ghi )perylene
benzo(ghi )perylene-d^2
biphenyl (Appendix C)
btphenyl-d10
bi»(2-chloroethyl) ether
bi»(2-chloroethyl> ether-dg
bis(2-chloroethoxy)methane
bis(2-chloroethoxy)methane (3)
bU(2-chloroisopropyl) ether
bi«(2-chloroisopropyl)ether-d12
bte(2-«thylhexyl) phthalate
bfs(2-ethylhexyl) phthalate-d^
4-bronophenyl phenyl ether
4-bromophenylphenyl ether-dg(3)
butyl benzyl phthalate
butyl benzyl phthalate-d^ (3)
n*C10 (Appendix C)
n-C10-d-_
n-C12 (Appendix C)
n-C12-d26
n-CU (Appendix C) (3)
n-C16 (Appendix C)
n-C16-dL,
n-C18 (Appendix C) (3)
n-C20 (Appendix C)
n-C20-d,2
n-C22 (Appendix C) (3)
n-C24 (Appendix C)
n-C24-cL0
n-C26 (Appendix C) (3>
s
21
38
38
31
41
49
119
269
20
41
183
168
26
114
26
24
21
45
41
43
34
33
27
33
17
27
31
29
44
52
31
29
51
70
74
53
109
33
46
39
59
34
31
11
28
35
X
79 •
38 -
69 •
39 •
58 -
31 •
16 -
ns(2)
65 •
25 -
32 -
11 -
59 -
15 -
62 -
35 -
72 •
29 •
75 •
28 -
55 -
29 -
43 -
29 -
81 -
35 •
69 •
32 -
44 -
40 -
19 -
32 •
24 -
ns -
35 -
ns •
ns -
80 -
37 -
42 -
53 •
34 -
45 -
80 -
27 •
35 -
Labeled
compound
recovery
(Sec 8.3
and 14.2)
P (%)
134
147
186
146
174
194
518
ns
168
298
545
577
143
514
195
181
160
268
148
165
196
196
153
196
138
149
220
205
140
161
233
205
195
298
369
331
ns
162
162
131
263
172
152
139
211
193
20
23
14
ns
12
ns
ns
21
14
ns
15
15
20
18
19
18
ns
ns
18
19
15
- 270
• 239
- 419
- ns
- 605
• ns
• ns
- 290
- 529
• ns
- 372
- 372
- 260
- 364
• 325
• 364
• ns
• ns
- 308
• 306
- 376
Calibration
verification
(Sec 12.5)
80 -
71 •
60 -
66 -
60 •
58 -
34 •
ns -
70 -
28 -
61 -
14 •
13 -
13 -
78 •
12 •
69 -
13 -
58 -
52 •
61 -
52 -
44 -
52 -
67 -
44 -
76 -
43 -
52 -
57 -
22 •
43 -
42 -
44 -
60 -
41 •
37 -
72 -
54 -
40 -
54 -
62 -
40 •
65 -
50 •
26 -
125
141
166
152
168
171
296
ns
142
357
164
ns
ns
ns
129
ns
145
ns
171
192
164
194
228
194
148
229
131
232
193
175
450
232
235
227
166
242
268
138
186
249
184
162
249
154
199
392
Labeled
and native
compound
on- going
accuracy
(Sec 12.7)
R (uq/L)
72 -
30 -
61 -
33 -
50 -
23 •
11 -
ns -
62 -
22 -
20 -
ns -
53 -
ns •
59 •
32 -
58 -
25 -
62 -
17 -
50 -
25 •
39 -
25 -
77 -
30 •
64 -
28 •
35 -
29 •
35 -
28 -
19 •
ns •
29 -
ns •
ns •
71 -
28 -
35 -
46 •
29 -
39 -
78 -
25 -
31 -
144
180
207
168
199
242
672
ns
176
329
ns
ns
155
685
206
194
168
303
176
267
213
222
166
222
145
169
232
224
172
212
170
224
237
504
424
408
ns
181
202
167
301
198
195
142
229
212
50
-------
Table 10 (continued)
ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS
EGD
No.
(1)
525
726
626
728
628
320
220
322
222
324
224
340
240
376
276
713
613
382
282
705
605
704
604
368
268
325
225
326
226
327
227
328
228
331
231
370
270
334
234
371
271
359
259
335
235
336
236
Labeled and
native compound
initial precision
and accuracy
' (Sec 8.2.3) (ua/L)
Comoound
n-C28 (Appendix C) (3)
n-C30 (Appendix C)
n-C30-d62
carbazole (4c)
carbazole-dg (3)
2-chloronaphthalene
2-chloronaphthalene-d~
4-chloro-3-methylphenol
4-chloro-3-methylphenol-d2
2-chlorophenol
2-chlorophenol -d.
4-chlorophenyl phenyl ether
4-chlorophenyl phenyl ether-dj
chrysene
chrysene-d,.-
p-cymene (Appendix C)
p-cymene-d14
dibenzo(a, h ) anthracene
dibenzo(a,h)anthracene-d.4 (3)
dibenzofuran (Appendix C)
dibenzofuran-dg
dibenzothiophene (Synfuel)
dibenzothiophene-da
di-n-butyl phthalate
di-n- butyl phthalate-d.
1 ,2-dichlorobenzene
1 ,2-dichlorobenzene-d.
1 ,3-dichlorobenzene
1 ,3-dichlorobenzene-d4
1 , 4 - d i ch 1 orobenzene
1 ,4-dichlorobenzene-d.
- 3,3'-dichlorobenzidine
3,3' -dichlorobenzidine-d6
2,4-dichlorophenol
2,4-dichlorophenol-d,
diethyl phthalate
diethyl phthalate-d.
2,4-dimethylphenol
2,4-dimethylphenol -d,
dimethyl phthalate
dimethyl phthalate-d4
2,4-dinitrophenol
2,4-dinitrophenol -d,
2,4-dinitrotoluene
2,4-dinitrotoluene-dj
2,6-dinitrotoluene
2,6-dinitrotoluene-dj
s
35
32
41
38
31
100
41
37
111
13
24
42
52
51
69
18
67
55
45
20
31
31
31
15
23
17
35
43
48
42
48
26
80
12
28
44
78
13
22
36
108
18
66
18
37
30
59
X
35 -
61 -
27 -
36 -
48 -
46 -
30 -
76 •
30 •
79 -
36 -
75 •
40 -
59 •
33 •
76 -
ns -
23 -
29 -
85 -
47 •
79 •
48 -
76 -
23 -
73 -
14 -
63 -
13 •
61 -
15 -
68 -
ns -
85 -
38 -
75 -
ns -
62 •
15 •
74 -
ns •
72 -
22 -
75 -
22 -
80 -
44 -
193
200
242
165
130
357
168
131
174
.135
162
166
161
186
219
140
359
299
268
136
136
150
130
165
195
146
212
201
203
194
193
174
562
131
164
196
260
153
228
188
640
134
308
158
245
141
184
Labeled
compound
recovery
(Sec 8.3
and 14.2)
P (%
13 -
29 -
15 -
ns -
23 -
19 -
13 -
ns -
14 -
28 -
29 -
13 -
ns •
ns •
ns •
ns •
24 -
ns -
ns •
ns -
ns -
10 -
17 •
Calibration
verification
(Sec 12.5)
) (ufl/mL)
479
215
324
613
255
325
512
ns
529
220
215
346
494
550
474
ns
260
ns
449
ns
ns
514
442
26 -
66 -
24 -
44 •
69 -
58 -
72 -
85 -
68 -
78 -
55 •
71 •
57 -
70 •
24 •
79 -
66 -
13 -
13 -
73 -
66 -
72 •
69 -
71 -
52 -
74 -
61 •
65 •
52 •
62 -
65 •
77 •
18 -
67 -
64 -
74 •
47 •
67 •
58 -
73 -
50 -
75 -
39 -
79 -
53 -
55 -
36 -
392
152
423
227
145
171
139
115
147
129
180
142
175
142
411
127
152
761
ns
136
150
140
145
142
192
135
164
154
192
161
153
130
558
149
157
135
211
150
172
137
201
133
256
127
187
183
278
Labeled
and native
compound
on-going
accuracy
(Sec 12.7)
R (uq/L)
31 -
56 •
23 -
31 -
40 -
35 -
24 -
62 -
14 -
76 -
33 •
63 -
29 -
48 -
23 •
72 -
ns -
19 •
25 -
79 -
39 -
70 -
40 •
74 •
22 •
70 •
11 •
55 •
ns •
53 -
11 •
64 •
ns •
83 -
34 -
65 -
ns -
60 -
14 -
67 -
ns -
68 -
17 -
72 -
19 -
70 -
31 •
212
215
274
188
156
442
204
159
314
138
176
194
212
221
290
147
468
340
303
146
160
168
156
169
209
152
247
225
260
219
245
185
ns
135
182
222
ns
156
242
207
ns
141
378
164
275
159
250
51
-------
Table 10 (continued)
ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS
EGO
Ho.
(1)
369
269
707
607
708
608
337
237
339
239
380
280
309
209
352
252
312
212
353
253
083
354
254
360
260
355
255
702
602
356
256
357
257
358
258
361
261
363
263
362
262
364
264
381
281
365
265
Labeled and
native compound
initial precision
and accuracy
(Sec 8.2.3) (us/I)
Compound
di-n-oetyl phthalate
di-n-octyl phthalate-d^
diphenylamine (Appendix C)
diphenylamine-d.g
diphenyl ether (Appendix C)
diphenyl ether-d^g
1 , 2-diphenylhydrazf ne
1,2-diphenylhydrazine-d10
fluoranthene
ftuoranthene-d.Q
fluorene
fluorene-d.jQ
hexachlorobenzene
hexachlorobenzene- Cfi
hexach lorobutadi ene
hexachlorobutadiene- C,
hexachloroethane _
hexachloroethane- C
hexachlorocyclopentadiene
hexachlorocyclopentadiene- C^
ideno(1,2,3-cd)pyrene (3)
isophorone
isophorone-dg
2-methyl-4,6-dinitrophenol
2-*»thyl-4,6-dinitrophenol-d2
naphthalene
naphthalene-dg
beta-naphthylamine (Appendix C)
beta-naphthylamine-d^
nitrobenzene
ni trobenzene-dg
2-nitrophenol
2-nitrophenol-d^
4-nitrophenol
4-ni trophenol -d.
H-nitrosodiraethylamine
H-nitrosodiraethylaraine-d6 (3)
H-nitrosodi-n-propylamine
H-nitrosodi-n-propylamine (3)
H-nitrosodiphenylamine
N-nitro8odiphenylamine-d6
pentachlorophenol
pentachlorophenol- Cfi
phenanthrene
phenanth rene - d^ g
phenol
phenol -de
s
16
46
45
42
19
37
73
35
33
35
29
43
16
81
56
63
227
77
15
60
55
25
23
19
64
20
39
49
33
25
28
15
23
42
188
49
33
45
37
45
37
21
49
13
40
36
161
77
12
58
27
82
36
49
31
71
36
81
51
90
36
51
ns
21
ns
69
ns
23
76
49
77
36
80
28
10
ne
69
18
78
41
62
14
10
ns
65
54
65
54
76
37
93
45
77
21
X
- 161
- 383
- 205
- 206
- 136
- 155
- 308
- 173
- 177
- 161
- 132
• 131
- 124
- 228
- 251
- 316
• ns
- 400
- 144
- ns
- 299
- 156
- 133
• 133
- 247
- 139
* 157
- ns
- ns
• 161
- 265
- 140
- 145
- 146
• 398
- ns
- ns
• 142
- 126
- 142
- 126
- 140
- 212
- 119
- 130
• 127
- 210
Labeled
compound
recovery
(Sec 8.3
and 14.2)
Calibration
verification
(Sec 12.5)
P (%) (ua/nrt.)
ns
11
19
17
20
27
13
ns
ns
ns
33
16
14
ns
ns
27
ns
ns
26
26
18
24
ns
- ns
- 488
• 281
- 316
• 278
- 238
• 595
- ns
- ns
• ns
• 193
- 527
- 305
- ns
• ns
- 217
- ns
• ns
- 256
- 256
- 412
- 241
• ns
71 •
21 -
57 •
59 -
83 -
77 •
75 •
58 -
67 •
47 -
74 •
61 -
78 -
38 -
74 -
68 •
71 •
47 -
77 •
47 -
13 -
70 •
52 •
69 -
56 -
73 •
71 -
39 •
44 -
85 -
46 -
77 •
61 -
55 -
35 •
39 •
44 -
68 -
59 •
68 •
59 -
77 -
42 •
75 •
67 -
65 -
48 -
140
467
176
169
120
129
134
174
149
215
135
164
128
265
135
148
141
212
129
211
761
142
194
145
177
137
141
256
230
115
219
129
163
183
287
256
230
148
170
148
170
130
237
133
149
155
208
Labeled
and native
compound
on- going
accuracy
(Sec 12.7)
R (Ufl/L)
74 -
10 •
51 -
21 -
77 -
29 -
40 -
26 •
64 -
30 -
70 -
38 -
85 -
23 -
43 -
ns -
13 •
ns •
67 -
ns •
19 •
70 -
'44 •
72 -
28 -
75 -
22 -
ns -
ns •
65 -
15 •
75 -
37 -
51 -
ns -
ns •
ns -
53 •
40 •
53 •
40 -
71 -
29 -
87 •
34 •
62 -
ns -
166
433
231
249
144
186
360
200
194
187
151
172
132
321
287
413
ns
563
148
ns
340
168
147
142
307
149
192
ns
ns
169
314
145
158
175
ns
ns
ns
173
166
173
166
150
254
126
168
154
ns
52
-------
Table 10 (continued)
ACCEPTANCE CRITERIA FOR PERFORMANCE TESTS
EGO
No.
(1)
703
603
384
284
710
610
709
609
729
629
308
208
530
731
631
321
221
Labeled and
native compound
initial precision
and accuracy
(Sec 8.2.3) (ua/L)
Comoound
alpha-picoline (Synfuel)
alpha-picoline- d7
pyrene
pyrene-dig
styrene (Appendix C)
styrene-cL
alpha- terpineol (Appendix C>
alpha- terpineol -d.
1,2,3-trichlorobenzene (4c)
1,2,3-trichlorobenzene-dj (3)
1,2,4-trichlorobenzene
1,2,4-trichlorobenzene-d,
2,3,6- trichlorophenol (4c> (3)
2,4,5-trichlorophenol (4c>
2,4,5-trichlorophenol-d- (3)
2,4,6-trichlorophenol
2,4,6-trichlorophenol-d2
38
138
19
29
42
49
44
48
69
57
19
57
30
30
47
57
47
X
59 •
11 •
76 -
32 -
53 •
ns •
42 •
22 -
15 •
15 •
82 -
15 -
58 -
58 -
43 -
5?, -
43 -
Labeled
compound
recovery
(Sec 8.3
and 14.2)
p m
149
380
152
176
221
281
234
292
229
212
136
212
137
137
183
205
183
ns
18
ns
ns
ns
ns
21
21
• ns
- 303
- ns
- 672
- 592
-592
- 363
- 363
Calibration
verification
(See 12.5)
60 -
31 -
76 •
48 -
65 -
44 -
54 -
20 -
60 -
61 -
78 -
61 -
56 -
56 -
69 •
81 •
69 -
165
324
132
210
153
228
186
502
167
163
128
163
180
180
144
123
144
Labeled
and native
compound
on- going
accuracy
(Sec 12.7)
R (US
50 -
ns •
72 -
28 •
48 •
ns -
38 -
18 -
11 -
10 -
77 -
10 •
51 •
51 •
34 -
48 •
34 -
I/L)
174
608
159
196
244
348.
258
339
297
282
144
282
153
153
226
244
226
(2)
Reference numbers beginning with 0, 1 or 5 indicate a pollutant quantified by the internal standard
method; reference numbers beginning with 2 or 6 indicate a labeled compound quantified by the internal
standard method; reference numbers beginning with 3 or 7 indicate a pollutant quantified by isotope
dilution.
ns » no specification: limit is outside the range that can be measured reliably.
This compound is to be determined by internal standard; specification is derived from related
compound.
For example, if P » 90X and s •» 10% for
five analyses of compost, the accuracy
interval is expressed as 70 - 11 OX.
Update the accuracy assessment for each
compound in each matrix on a regular basis
(e.g. after each 5-10 new accuracy
measurements).
8.5 Blanks--reagent water and high solids
reference matrix blanks are analyzed to
demonstrate freedom from contamination.
8.5.1 Extract and concentrate a one liter
reagent water blank or a high solids
reference matrix blank with each sample
lot (samples started through the
extraction process on the same 8 hr shift,
to a maximum of 20 samples). Analyze the
blank immediately after analysis of the
precision and recovery standard (Section
6.14) to demonstrate freedom from
contamination.
8.5.2 If any of the compounds of interest
(Tables 1 - 4) or any potentially
interfering compound is found in an
aqueous blank at greater than 10 ug/L, or
in a high solids reference matrix blank at
greater than 100 ug/kg (assuming a
response factor of 1 relative to the
internal standard for compounds not listed
in Tables 1 - 4), analysis of samples is
halted until the source of contamination
is eliminated and a blank shows no
evidence of contamination at this level.
8.6 The specifications contained in this
method can be met if the apparatus used is
calibrated properly, then maintained in a
calibrated state. The standards used for
calibration (Section 7), calibration
verification (Section 12.5), and for
initial (Section 8.2) and on-going
(Section 12.7) precision and recovery
should be identical, so that the most
53
-------
precise results Hill be obtained. The
OCXS instrument in particular will.provide
the most reproducible results if dedicated
to the settings and conditions required
for the analyses of semivolatiles by this
method.
8.7 Depending on specific program require-
ments, field replicates may be collected
to determine the precision of the sampling
technique, and spiked samples may be
required to determine the accuracy of the
analysis when the internal standard method
is used.
9 SAMPLE COLLECTION, PRESERVATION, AND
HANDLING
9.1 Collect sanples in glass containers
following conventional sampling practices
(Reference 8). Aqueous samples which flow
freely are collected in refrigerated
bottles using automatic sampling
equipment. Solid samples are collected as
grab sanples using wide mouth jars.
9.2 Maintain samples at 0 - 4 °C from the time
of collection until extraction. If
residual chlorine is present in aqueous
samples, add 80 mg sodium thiosulfate per
liter of water. EPA methods ,330.4 and
330.5 may be used to measure residual
chlorine (Reference 9).
9.3 Begin sample extraction within seven days
of collection, and analyze all extracts
within 40 days of extraction.
10 SAMPLE EXTRACTION, CONCENTRATION, AND
CLEANUP
Samples containing one percent solids or
less are extracted directly using
continuous liquid/liquid extraction
techniques (Section 10.2.1 and Figure 4).
Staples containing one to 30 percent
solids are diluted to the one percent
level with reagent water (Section 10.2.2)
and extracted using continuous
liquid/liquid extraction techniques.
Sanples containing greater than 30 percent
solids are extracted using ultrasonic
techniques (Section 10.2.5)
10.1 Determination of percent solids
10.1.1 Weigh 5 - 10 g of sample into a tared
beaker.
10.1.2 Dry overnight (12 hours minimum) at 110 t
5 *C, and cool in a dessicator.
10.1.3 Determine percent solids as follows:
X solids =' weight of dry sample x 100
weight of wet sample
10.2 Preparation! of samples for extraction
10.2.1 Sanples containing one percent solids or
less—extract sample directly using
continuous liquid/liquid extraction
techniques.
10.2.1.1 Measure 1.00 ± 0.01 liter of sample into a
clean 1.5 - 2.0 liter beaker.
10.2.1.2 Dilute aliquot—for samples which are
expected 1:0 be difficult to extract,
concentrate, or clean-up, measure an
additional 100.0 ± 1.0 mL into a clean 1.5
- 2.0 liter beaker and dilute to a final
volume of 1.00 ± 0.1 liter with reagent
water.
10.2.1.3 Spike 0.5 mL of the labeled compound
spiking solution (Section 6.8) into the
sample aliquots. Proceed to preparation
of the QC aliquots for low solids samples
(Section 10.2.3).
10.2.2 Samples containing one to 30 percent
solids
10.2.2.1 Mix sample thoroughly.
10.2.2.2
10.2.2.3
10.2.2.4
Using the percent solids found in 10.1.3,
determine the weight of sample required to
produce one liter of solution containing
one percent solids as follows:
sample weight
1000
X solids
grains
Discard all sticks, rocks, leaves and
other foreign material prior to weighing.
Place the weight determined in 10.2.2.2 in
a clean 1.15 - 2.0 liter beaker.
Dilute aliquot—for sanples which are
expected to be difficult to extract,
concentrate, or clean up, weigh an amount
of sample equal to one-tenth the amount
determined in 10.2.2.2 into a second clean
54
-------
[10.2.3.1]
[10.2.1.3, 10.2.3.2]
[10.2.3.3]
[10.2.4]
[10.3.2]
[10.3.4]
[10.5]
[10.6]
[11.3]
[11.4]
STANDARD
1 L REAGENT
WATER
SPIKE
1.0 mL
OF STANDARDS
STIR AND
EQUILIBRATE
STANDARD OR BLANK
EXTRACT BASE/
NEUTRAL
ORGANIC | AQUEOUS
EXTRACT ACID
CONCENTRATE
TO 2-4 mL
CONCENTRATE
TO 2-4 mL
CONCENTRATE
TOLOmL
ADD INTERNAL
STANDARD
INJECT
BLANK
1 L REAGENT
WATER
SPIKE 500 jjL
OF 200 pg/mL
ISOTOPES
STIR AND
EQUILIBRATE
SAMPLE
1 L ALIQUOT
SPIKE 500 pL
OF 200 pg/mL
ISOTOPES
STIR AND
EQUILIBRATE
J,
EXTRACT BASE/
NEUTRAL
ORGANIC
AQUEOUS
EXTRACT ACID
CONCENTRATE
TO 1.0 mL
CONCENTRATE
TOLOmL
ADD INTERNAL
STANDARD
ADD INTERNAL
STANDARD
INJECT
INJECT
FIGURE 4 Flow Chart for Extraction/Concentration of Low Solids Precision and Recovery Standard, Blank, and
Sample by Method 1625.. Numbers in Brackets [ ] Refer to Section Numbers in the Method.
55
-------
1.5 - 2.0 liter beaker. Mien diluted to
1.0 liter, this ' dilute aliquot will
contain 0.1 percent solids.
10.2.2.5 Bring the sample aliquot(s) above to 100 -
200 Ki. volume with reagent water.
10.2.2.6 Spike 0.5 mL of the labeled compound
spiking solution (Section 6.8) into each
sample aliquot.
10.2.2.7 Using a clean metal spatula, break any
solid portions of the sample into small
pieces.
10.2.2.8 Place the 3/4 inch horn on the ultrasonic
probe epprox 1/2 inch below the surface of
each sample aliquot and pulse at 50
percent for three minutes at full power.
If necessary, remove the probe from the
solution and break any large pieces using
the metal spatula or a stirring rod and
repeat the sonication. Clean the probe
with methylene chloride:acetone (1:1)
between samples to preclude cross-
contamination.
10.2.2.9 Bring the sample volume to 1.0 ± 0.1 liter
with reagent water.
10.2.3 Preparation of QC aliquots for samples
containing low solids <<30 percent).
10.2.3.1 For each sample or sample lot (to a
maximum of 20) to be extracted at the same
time, place three 1.0 ± o'.01 liter
aliquots of reagent water in clean 1.5 -
2.0 liter beakers.
10.2.3.2 Spike 0.5 mL of the labeled compound
spiking solution (Section 6.8; ,into one
reagent water aliquot. This aliquot will
serve as the blank.
10.2.3.3 Spike 1.0 mL of the precision and recovery
standard (Section 6.14) into the two
remaining reagent water aliquots.
10.2.4 Stir and equilibrate all sample and QC
solutions for 1-2 hours. Extract the
samples and QC aliquots per Section 10.3.
10.2.5 Samples containing 30 percent solids or
greater
10.2.5.1 Mix the sample thoroughly
10.2.5.2 Discard all. sticks, rocks, leaves and
other foreign material prior to weighing.
Weigh 30 ± 0.3 grams into a clean 400 -
500 mL beaker.
10.2.5.3 Dilute aliquot—for samples which are
expected to be difficult to extract,
concentrate,, or clean-up, weigh 3 ± 0.03
grams into a clean 400 - 500 ml beaker.
10.2.5.4 Spike 0.5 mL of the labeled compound
spiking solution (Section 6.8) into each
sample aliquot.
10.2.5.5 QC aliquots--for each sample or sample lot
(to a maximum of 20) to be extracted at
the same time, place three 30 ± 0.3 gram
aliquots of the high solids reference
matrix in clean 400 - 500 mL beakers.
10.2.5.6 Spike 0.5 mL of the labeled compound
spiking solution (Section 6.8) into one
high solids reference matrix aliquot.
This aliquot will serve as the blank.
10.2.5.7 Spike 1.0 ml. of the precision and recovery
standard (Section 6.14) into the two
remaining high solids reference matrix
aliquots. Extract, concentrate, and clean
up the high solids samples and QC aliquots
per Sections 10.4 through 10.8.
10.3 Continuous extraction of low solids
(aqueous) samples--piace 100 - 150 mL
methylene chloride in each continuous
extractor and 200 - 300 mL in each
distilling flask.
10.3.1 Pour the sample(s), blank, and QC aliquots
into the extractors. Rinse the glass
containers with 50 - 100 mL methylene
chloride and add to the respective
extractors. Include all solids in the
extraction process.
10.3.2 Base/neutral extraction—adjust the pH of
the waters in the extractors to 12 - 13
with 6N NaOH while monitoring with a pH
meter. Begin the extraction by heating
the flask until the methylene chloride is
boiling. Uhen properly adjusted, 1 - 2
drops of methylene chloride per second
will fall from the condenser tip into the
water. Test and adjust the pH of the
waters during the first to second hour and
during the fifth to tenth hour of
extraction. Extract for 24 - 48 hours.
56
-------
10.3.3 Remove the distilling flask, estimate and
record the volune of extract (to the
nearest 100 mL), and pour the contents
through a drying column containing 7 to 10
cm anhydrous sodium sulfate. Rinse the
distilling flask with 30 - 50 ml of
methylene chloride and pour through the
drying column. Collect the solution in a
500 ml K-D evaporator flask equipped with
a 10 mL concentrator tube. Seal, label as
the base/neutral fraction, and concentrate
per Sections 10.5 to 10.6.
10.3.4 Acid extraction—adjust the pH of the
waters in the extractors to 2 or less
using 6N sulfuric acid. Charge clean
distilling flasks with 300 • 400 ml of
methylene chloride. Test and adjust the
pH of the waters during the first 1 - 2 hr
and during the fifth to tenth hr of
extraction. Extract for 24 - 48 hours.
Repeat Section 10.3.3, except label as the
acid fraction.
10.4 Ultrasonic extraction of high solids
samples
10.4.1 Add 60 grams of anhydrous sodium sulfate
the sample and QC aliquot(s) (Section
10.2.5) and mix thoroughly.
10.4.2 Add 100 ± 10 mL of acetonermethylene
chloride (1:1) to the sample and mix
thoroughly.
10.4.3 Place the 3/4 in. horn on the ultrasonic
probe approx 1/2 in. below the surface of
the solvent but above the solids layer and
pulse at 50 percent for three minutes at
full power. If necessary, remove the
probe from the solution and break any
large pieces using the metal spatula or a
stirring rod and repeat.the sonication.
10.4.4 Decant the extracts through Whatman 41
filter paper using glass funnels and
collect in 500 - 1000 ml graduated
cylinders.
10.4.5 Repeat the extraction steps (10.4.2 -
10.4.4) twice more for each sample and QC
aliquot. On the final extraction, swirl
the sample or QC aliquot, pour into its
respective glass funnel, and rinse with
acetoneimethylene chloride. Record the
total extract volume.
10.4.6 Pour each extract through a drying column
containing 7 to 10 cm of anhydrous sodium
sulfate. Rinse the graduated cylinder
with 30 - 50 mL of methylene chloride and
pour through the drying column. Collect
each extract in a 500 mL K-D evaporator
flask equipped with a 10 mL concentrator
tube. Seal and label as the high solids
semivolatile fraction. Concentrate and
clean up the samples and QC aliquots per
Sections 10.5 through 10.8.
10.5 Macro concentration—concentrate the
extracts in separate 500 mL K-D flasks
equipped with 10 mL concentrator tubes.
10.5.1 Add 1 to 2 clean boiling chips to the
flask and attach a three-ball macro Snyder
column. Prewet the column by adding
approx one mL of methylene chloride
through the top. Place the K-D apparatus
in a hot water bath so that the entire
lower rounded surface of the flask is
bathed with steam. Adjust the vertical
position of the apparatus and the water
temperature as required to complete the
concentration in 15 to 20 minutes. At the
proper rate of distillation, the balls of
the column will actively chatter but the
chambers will not flood. When the liquid
has reached an apparent volume of 1 mL,
remove the K-D apparatus from the bath and
allow the solvent to drain and cool for at
least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joint
into the concentrator tube with 1 - 2 mL
of methylene chloride. A 5 mL syringe is
recommended for this operation.
10.5.2 For performance standards (Sections 8.2
and 12.7) and for blanks (Section 8.5),
J combine 'the acid and base/neutral extracts
for each at this point. Do not combine
the acid and base/neutral extracts for
aqueous samples.
10.6 Micro-concentration
10.6.1 Kuderna-Danish (K-D)--add a clean boiling
chip and attach a two-ball micro Snyder
column to the concentrator tube. Prewet
the column by adding approx 0.5 mL
methylene chloride through the top. Place
the apparatus in the hot water bath.
Adjust the vertical position and the water
temperature as required to complete the
concentration in 5-10 minutes. At the
proper rate of distillation, the balls of
57
-------
the column will actively chatter but the
chambers will not flood. When the liquid
reaches an apparent volume of approx 0.5
mL, remove the apparatus from the water
bath and allow to drain and cool for at
least 10 Minutes. Remove the micro Snyder
column and rinse its lower joint into the
concentrator tube with approx 0.2 mL of
methylene chloride. Adjust the final
volume to 5.0 mL if the extract is to be
cleaned up by GPC, to 1.0 mL if it does
not require clean-up, or to 0.5 mL if it
has been cleaned up.
10.6.2 Nitrogen blowdown--Place the concentrator
tube in a warm water bath (35 *C) and
evaporate the solvent volume using a
gentle stream of clean, dry nitrogen
(filtered through a column of activated
carbon). Caution; New plastic tubing
Must not be used between the carbon trap
and the sample, since it may introduce
interferences. The internal wall of the
tube must be rinsed down several times
with methylene chloride during the
operation. During evaporation, the tube
solvent level must be kept below the water
level of the bath. The extract must never
be allowed to become dry. Adjust the
final volume to 5.0 mL if the extract is
to be cleaned up by GPC, to 1.0 mL if it
does not require clean-up, or to 0.5 mL if
it has been cleaned up.
10.7 Transfer the concentrated extract to a
clean screw-cap vial. Seal thevvial with a
Teflon-lined lid, and mark the level on
the vial. Label with the sample number and
fraction, and store in the dark at -20 to
-10 *C until ready for analysis.
10.8 GPC setup and calibration
10.8.1 Column packing
10.8.1.1 Place 75 ± 5 g of SX-3 Bio-beads in a 400
- 500 mL beaker.
10.8.1.2 Cover the beads and allow to swell
overnight (12 hours minimum).
10.8.1.3 Transfer the swelled beads to the column
and punp solvent through the column, from
bottom to top, at 4.5 - 5.5 mL/min prior
to connecting the column to the detector.
10.8.1.4 After purging the column with solvent for
1-2 hours, adjust the column head
10.8.2
10.8.2.1
10.8.2.2
10.8.2.3
10.8.2.4
10.8.2.5
10.9
10.9.1
10.9.2
10.9.3
10.9.4
10.9.5
pressure to 7 - 10 psig, and purge for 4 -
5 hours to remove air from the column.
Maintain a head pressure of 7 - 10 psig.
Connect the column to the detector.
Column calibration
Load 5 ml of the calibration solution
(Section 6.4) into the sample loop.
Inject the calibration solution and record
the signal from the detector. The elution
pattern will be corn oil, bis(2-
ethylhexyl) phthalate, pentachlorophenol,
perylene, and sulfur.
Set the "dump time" to allow >85% removal
of the corn oil and >85% collection of the
phthalate.
Set the "collect time" to the peak minimum
between perylene and sulfur.
Verify the calibration with the
calibration solution after every 20
extracts. Calibration is verified if the
recovery of the pentachlorophenol is
greater than 85%. If calibration is not
verified, the system shall be recalibrated
using the calibration solution, and the
previous 20 samples shall be re-extracted
and cleaned up using the calibrated GPC
system.
Extract cleanup
Filter the extract or load through the
filter holder to remove particulates.
Load the 5.0 mL extract onto the column.
The maximum capacity of the column is 0.5
- 1.0 'gram. If necessary, split the
extract into multiple aliquots to prevent
column overload.
Elute the extract using the calibration
data determined in 10.8.2. Collect the
eluate in a clean 400 - 500 ml beaker.
Concentrate the cleaned up extract to 5.0
mL per Section 10.5.
Rinse the sample loading tube thoroughly
with methylene chloride between extracts
to prepare: for the next sample.
If a particularly dirty extract is
encountered, a 5.0 mL methylene chloride
58
-------
blank shall be run through the system to
check for carry-over.
10.9.6 Concentrate the extract to 0.5 mL and
transfer to a screw-cap vial per Sections
10.6 and 10.7. Concentrating extracts
cleaned up by GPC to 0.5 mL will place the
analytes in the same part of the GCHS
calibration range as in samples not
subjected to CPC.
11 GCHS ANALYSIS
11.1 Establish the operating conditions given
in Tables 5 or 6 for analysis of the
base/neutral , or acid extracts, respec-
tively. For analysis of combined extracts
(Section 10.5.2 and 10.9.6), use the
operating conditions in Table 5.
11.2 Bring the concentrated extract (Section
10.7) or standard (Sections 6.13 - 6.14)
to room temperature and verify that any
precipitate has redissolved. Verify the
level on the extract (Sections 6.6 and
10.7) and bring to the mark with solvent
if required.
11.3 Add the internal standard solution
(Section 6.10) to the extract (use 1.0 uL
of solution per 0.1 mL of extract)
immediately prior to injection to minimize
the possibility of loss by evaporation,
adsorption, or reaction. Nix thoroughly.
11.4 Inject a volume of the standard solution
or extract such that 100 ng of the
internal standard will be injected, using
on-colum or split less injection. For 1
mL extracts, this volume Mill be 1.0 uL.
Start the GC column initial isothermal
hold upon injection. Start MS data
collection after the solvent peak elutes.
Stop data collection after the
benzo(ghi)perylene or pentachlorophenol
peak elutes for the base/neutral (or semi-
volatile) or acid fraction, respectively.
Return the column to the initial
temperature for analysis of the next
sample.
12 SYSTEM AND LABORATORY PERFORMANCE
12.1 At the beginning of each 8 hr shift during
which analyses are performed, GCHS system
performance and calibration are verified
for all pollutants and labeled compounds.
For these tests, analysis of the 100 ug/mL
calibration standard (Section 6.13) shall
be used to verify all performance
criteria. Adjustment and/or recall'brat ion
(per Section 7) shall be performed until
all performance criteria are met. Only
after all performance criteria are met may
samples, blanks, and precision and
recovery standards be analyzed.
12.2 DFTPP spectrum validity-inject 1 uL of
the DFTPP solution (Section 6.11) either
separately or within a few seconds of
injection of the standard (Section 12.1)
analyzed at the beginning of each shift.
The criteria in Table 7 shall be met.
12.3 Retention times—the absolute retention
time of 2,2'-difluorobiphenyl shall be
within the range of 1078 to 1248 seconds
and the relative retention times of all
pollutants and labeled compounds shall
fall within the limits given in Tables 5
and 6.
12.4 GC resolution—the valley height between
anthracene and phenanthrene at m/z 178 (or
the analogs at m/z 188) shall not exceed
10 percent of the taller of the two peaks.
12.5 Calibration verification—compute the
concentration of each pollutant (Tables 1
and 2) by isotope dilution (Section 7.4)
for those compounds which have labeled
analogs. Compute the concentration of
each pollutant which has no labeled analog
' >by the internal standard method (Section
7.5). Compute the concentration of the
labeled compounds by the internal standard
1 ''method. These concentrations are computed
based' on the calibration data determined
in Section 7.
12.5.1 For each pollutant and labeled compound
being tested, compare the concentration
with the calibration verification limit in
Table 10. If all compounds meet the
acceptance criteria, calibration has been
verified and analysis of blanks, samples,
and precision and recovery standards may
proceed. If, however, any compound fails,
the measurement system is not performing
properly for that compound. In this
event, prepare a fresh calibration
standard or correct the problem causing
the failure and repeat the test (Section
12.1), or recalibrate (Section 7).
-------
12.6 Multiple peaks—each compound injected
shall give a single, distinct GC peak.
12.7 On-going precision arid accuracy.
12.7.1 Analyze the extract of one of the pair of
precision and recovery standards (Section
10} prior to analysis of samples from the
same lot.
12.7.2 Compute the concentration of each
pollutant (Tables 1 and 2) by isotope
dilution (Section 7.4) for those compounds
which have labeled analogs. Compute the
concentration of each pollutant which has
no labeled analog by the internal standard
method (Section 7.5). Compute the concen-
tration of the labeled compounds by the
internal standard method.
12.7.3 For each pollutant and labeled compound,
compare the concentration with the limits
for on-going accuracy in Table 10. If all
compounds meet the acceptance criteria,
system performance is acceptable and
analysis of blanks and samples may
proceed. If, however, any individual
concentration falls outside of the range
given, system performance is unacceptable
for that compound.
NOTE: The large number of compounds in
Table 10 present a substantial probability
that one or more will fail when all
compounds are analyzed. To determine, if
the extraction/concentration system is out
of control or if the failure is caused by
probability, proceed as follows:
12.7.3.1 Analyze the second aliquot of the pair of
precision and recovery standards (Section
10).
12.7.3.2 Compute the concentration of only those
pollutants or labeled compounds that
failed the previous test (Section 12.7.3).
If these compounds now pass, the
extraction/concentration processes are in
control and analysis of blanks and samples
may proceed. If, however, any of the same
compounds fail again, the extrac-
tion/concentration processes are not being
performed properly for these compounds.
In this event, correct the problem, re-
extract the sample lot (Section 10) and
repeat the on-going precision and recovery
test (Section 12.7).
12.7.4 Add results which pass the specifications
in Section 12.7.3 to initial and previous
on-going data for each compound in each
matrix. Update QC charts to form a
graphic representation of continued
laboratory performance (Figure 5).
Develop a statement of laboratory accuracy
for each pollutant and labeled compound in
each matrix type by calculating the
average percent recovery (R) and the
standard deviation of percent recovery
(sp). Express the accuracy as a recovery
interval from R - 2s to R + 2s . For
example, if R = 95% and sp = 5%, the
accuracy Is 85 - 105%.
45,000
35,000
25,000
1
I
I 1 1 1 I I 1 1
ANTHRACENE-D,,,
•~
• .
.
i i i i i i i i
-+3s
- 3s
3-45678
ANALYSIS NUMBER
9 10
l
il
1.10
1.00
0.90
i i
i "
i i i i i
ANTHRACENE
• _
> »
- + 3s
--3s
6/1 6/1 6/1 6/1 • 6/2 6/2 6/3 6/3 6/4 6/5
DATE ANALYZED
FIGURE 5 Quality Control Charts Showing Area
(top graph) and Relative Response of
Anthracene to Anthracene-d,0 (lower graph)
Plotted as a Function of Time or Analysis
Number.
13 QUALITATIVE DETERMINATION
Identification is accomplished by
comparison of data from analysis of a
sample or blank with data stored in the
mass spectral libraries. For compounds
for which the relative retention times and
mass spectra are known, identification is
confirmed per Sections 13.1 and 13.2. For
unidentified GC peaks, the spectrum is
compared to spectra in the EPA/NIH mass
spectral file per Section 13.3.
13.1 Labeled compounds and pollutants having no
labeled analog (Tables 1-4):
60
-------
13.1.1 The signals for all characteristic m/z's
stored in the spectral library (Section
7.2.4) shall be present and shall maximize
within the same two consecutive scans.
13.1.2 Either (1) the background corrected EICP
areas, or (2) the corrected relative
intensities of the mass spectral peaks at
the GC peak maximum shall agree within a
factor of two (0.5 to 2 times) for all
masses stored in the library.
13.1.3 For the compounds for which the system has
been calibrated (Tables 1 and 2), the
retention time shall be within the windows
specified in Tables 5 and 6, or within t
15 scans or t 15 seconds (whichever is
greater) for compounds for which no window
is specified.
13.1.4 The system has not been calibrated for the
compounds listed in Tables 3 and 4,
however, the relative retention times and
mass spectra of these compounds are known.
Therefore, for a compound in Tables 3 or 4
to be identified, its retention time
relative to the internal standard 2,2'-
difluorobiphenyl must fall within a
retention time window of ± 30 seconds, or
± 30 scans (whichever is greater) of the
nominal retention time of the compound
specified in Tables 5 or 6.
13.2 Pollutants having a labeled analog (Tables
1 and 2):
13.2.1 The signals for all characteristic m/z's
stored in the spectral library (Section
7.2.4) shall be present and shall maximize
within the same two consecutive scans.
13.2.2 Either (1) the background corrected EICP
areas, or (2) the corrected relative
intensities of the mass spectral peaks at
the GC peak maximum shall agree within a
factor of two for all masses stored in the
spectral library.
13.2.3 The relative retention- time between the
pollutant and its labeled analog shall be
within the windows specified in Tables 5
and 6.
13.3 Unidentified GC peaks
13.3.1 The signals for masses specific to a GC
peak shall all maximize within ± 1 scan.
13.3.2 Either (1) the background corrected EICP
areas, or (2) the corrected relative
intensities of the mass spectral peaks at
the GC peak maximum shall agree within a
factor of two with the masses stored in
the EPA/NIH Mass Spectral File.
13.4 The m/z's present in the experimental mass
spectrum that are not present in the
reference mass spectrum shall be accounted
for by contaminant or background ions. If
the experimental mass spectrum is
contaminated, or if identification is
ambiguous, an experienced spectrometrist
(Section 1.4) is to determine the presence
or absence of the compound.
14 QUANTITATIVE DETERMINATION
14.1 Isotope dilution—Because the pollutant
; and its labeled analog exhibit the same
effects upon extraction, concentration,
and gas chromatography, correction for
recovery of the pollutant can be made by
adding a known amount of a labeled
compound to every sample prior to
extraction. Relative response (RR) values
for sample mixtures are used in
conjunction with the calibration curves
described in Section 7.4 to determine
concentrations directly, so long as
labeled compound spiking levels are
constant. For the phenol example given in
Figure 1 (Section 7.4.1), RR would be
equal to 1.114. For this RR value, the
phenol, calibration curve given in Figure 1
indicates a concentration of 27 ug/mL in
14.2
the sample extract (C ).
Internal standard—compute the concentra-
, tion in the extract using the response
factor determined from calibration data
(Section 7.5) and the following equation:
Cex (ug/mL) =
(Ajs x F)
where C is the concentration of the
compound in the extract, and the other
terms are as defined in Section 7.5.1.
14.3 The concentration of the pollutant in the
solid phase of the sample is computed
using the concentration of the pollutant
in the extract and the weight of the
solids (Section 10), as follows:
61
-------
Concentration in solid (ug/kg)
where V is the extract volume in mL, and
U is the sample weight in kg.
14.4 Dilution of samples-- if the EICP area at
the quantitation m/z for any compound
exceeds the calibration range of the
system, the extract of the dilute aliquot
(Section 10) is analyzed by isotope
dilution. For water samples, where the
base/neutral and acid extracts are not
combined, re-analysis is only required for
the extract (B/H or A) in which the
compound exceeds the calibration range.
If further dilution is required and the
sample holding time has not been exceeded,
a smaller sample aliquot is extracted per
Section 14.4.1 - 14.4.3. If the sample
holding time has been exceeded, the sample
extract is diluted by successive factors
of 10, internal standard is added to give
a concentration of 100 ug/mL in the
diluted extract, and the diluted extract
is analyzed by the internal standard
method.
14.4.1 For samples containing one percent solids
or less for which the holding time has not
been exceeded, dilute 10 mL, 1.0 mL, 0.1
mL etc. of sample to one liter with
reagent water and extract per Section
10.2.1.
14.4.2 For samples containing 1-30 percent
solids for which the holding time has not
been exceeded, extract an amount of sample
equal to 1/100 the amount determined in
10.2.2.2. Extract per Section 10.2.2.
14.4.3 For samples containing 30 percent solids
or greater for which the holding time has
not been exceeded, extract 0.30 ± 0.003 g
of sample per Section 10.2.5.
14.5 Dilution of samples containing high
concentrations of compounds to be
identified per Section 13.3 -- When the
EICP area of the quant 1 tat ion m/z of a
compound to be identified per Section 13.3
exceeds the linear range of the GCMS
system, or when any peak is saturated,
dilute the sample per Section 14.4.1-
14.4.3.
14.6 Results are reported to three significant
figures for all pollutants, labeled
compounds, and tentatively identified
compounds found in all standards, blanks,
and samples. For aqueous samples, the
units are ug/L, and for samples containing
one percent solids or greater (soils,
sediments, filter cake, compost), the
units are ug/kg, based on the dry weight
of the solids.
14.6.1 Results for samples which have been
diluted are reported at the least dilute
level at which the area at the
quantitation m/z is within the calibration
range (Section 14.4), or at which no m/z
in the spectrum is saturated (Section
14.5). For compounds having a labeled
analog, results are reported at the least
dilute level at which the area at the
quantitation m/z is within the calibration
range (Section 14.4) and the labeled
compound recovery is within the normal
range for the method (Section 15.4).
15 ANALYSIS OF COMPLEX SAMPLES
15.1 Some samples may contain high levels
(>1000 ug/L) of the compounds of interest,
interfering compounds, and/or polymeric
materials., Some samples will not
concentrate to one mL (Section 10.6);
others will overload the GC column and/or
mass spectrometer.
15.2 Analyze the dilute aliquot (Section 10)
when the sample will not concentrate to
1.0 mL. If a dilute aliquot was not
extracted,, and the sample holding time
(Section 9.3) has not been exceeded,
dilute an aliquot of an aqueous sample
with reagent water, or weigh a dilute
aliquot of a high solids sample and re-
extract (Section 10); otherwise, dilute
the extract (Section 14.4) and analyze by
the internal standard method (Section
14.2).
15.3 Recovery of internal standard-- the EICP
area of the internal standard should be
within a factor of two of the area in the
shift standard (Section 12.1). If the
absolute areas of the labeled compounds
are within a factor of two of the
respective areas in the shift standard,
and the internal standard area is less
than one-half of its respective area, then
loss of the internal standard in the
62
-------
extract has occurred, in this case, use
one of the labeled compounds (preferably a
polynuclear aromatic hydrocarbon) to
compute the concentration of a pollutant
with no labeled analog.
15.4 Recovery of labeled compounds--in most
samples, labeled compound recoveries will
be similar to those from reagent water or
from the high solids reference matrix
(Section 12.7). If the labeled compound
recovery is outside the limits given in
Table 10, the extract from the dilute
aliquot (Section 10) is analyzed as* in
Section 14.4. If the recoveries of all
labeled compounds and , the internal
standard are low (per the criteria above),
then a loss in instrument sensitivity is
the most likely cause. In this case, the
100 ug/mL calibration standard (Section
12.1) shall be analyzed and calibration
verified (Section 12.5). If a loss in
sensitivity has occurred, the instrument
shall be repaired, the performance
specifications in Section 12 shall be met,
and the extract reanalyzed. If a loss in
instrument sensitivity has not occurred,
the method does not apply to the sample
being analyzed, and the result may not be
reported for regulatory compliance
purposes.
16 METHOD PERFORMANCE
16.1 Interlaboratory performance for this
method is detailed in Reference 10.
Reference mass spectra, retention times,
and response factors are from References
11 and 12. Results of initial tests of
this method on municipal sludge can be
found in Reference 13.
16.2 . A chromatogram of the 100 ug/mL
acid/base/neutral calibration standard
(Section 6.13) is shown in Figure 6.
"Working with
CDC, NIOSH;
1977).
Carcinogens," DHEW, PHS,
Publication 77-206, (Aug
REFERENCES
"Performance Tests for the Evaluation of
Computerized Gas Chromatography/Mass
Spectrometry Equipment and Laboratories"
USEPA, EHSL Cincinnati, Ohio 45268, EPA-
600/4-80-025 (April 1980).
National Standard Reference Data System,
"Mass Spectral Tape Format", US National
Bureau of Standards (1979 and later
attachments).
4 "OSHA Safety and Health Standards, General
Industry" OSHA 2206, 29 CFR 1910 (Jan
1976).
5 "Safety in Academic Chemistry
Laboratories," ACS Committee on Chemical
Safety (1979).
6 "Interlaboratory Validation of U. S.
Environmental Protection Agency Method
1625A, Addendum Report", SRI
International, Prepared for Analysis and
Evaluation Division (UH-557), USEPA, 401 M
St SU, Washington DC 20460 (January
1985).
7 "Handbook of Analytical Quality Control in
Water and Wastewater Laboratories," USEPA,
EMSL, Cincinnati, OH 45268, EPA-600/4-79-
019 (March 1979).
8 "Standard Practice for Sampling Water,"
ASTM Annual Book of Standards, ASTM,
Philadelphia, PA, 76 (1980).
9 "Methods 330.4 and 330.5 for Total
Residual Chlorine," USEPA, EMSL,
Cincinnati, OH 45268, EPA 600/4-70-020
(March 1979).
10 "Inter-laboratory Validation of US
Environmental Protection Agency . Method
1625," USEPA, Effluent Guidelines
Division, Washington, DC 20460 (June 15,
1984).
11 "Narrative for Episode 1036: Paragraph
4(c) Mass Spectra, Retention Times, and
Response Factors", U S Testing Co, Inc.
Prepared for W. A. Telliard, Industrial
Technology Division (WH-552), USEPA, 401 M
St SW, Washington DC 20460 (October 1985).
12 "Narrative for SAS 109: Analysis of
Extractable Organic Pollutant Standards by
Isotope Dilution GC/MS", S-CUBED Division
of Maxwell Laboratories, Inc., Prepared
for W. A. Telliard, Industrial Technology
Division (WH-552), USEPA, 401 M St SW,
Washington DC 20460 (July 1986).
13 Colby, Bruce N. and Ryan, Philip W.,
"Initial Evaluation of Methods 1634 and
1635 for the analysis of Municipal
Wastewater Treatment Sludges by Isotope
Dilution GCMS", Pacific Analytical Inc.,
Prepared for W. A. Telliard, Industrial
Technology Division (WH-552), USEPA, 401 M
St SW, Washington DC 20460 (July 1986).
63
-------
RIC DATA: ABNID116S ttl
63/13/84 5:24:80 CALI: ABH1D1166 #1
SAMPLE: AB,C,UER,eeiee,8e,C,NA:HA,NAS
CONOS.: 1625A,38M,e.25«1,5@38,3e-288e8,156280,38CM/SJ
RANGE: G 1,3280 LABEL: N 2, 3.8 QUAN: A 2, 2.8 J
SCANS 1 TO 3208
8 BASE: U 28, 3
715775.
1888
15:58
1588
23:45
2888
31:48
2588
39:35
3888
47:38
SCAN
TIME
FIGURE 6 Chromatogram of Combined Acid/Base/Neutral Standard.
64
-------
Appendix A
Mass Spectra in the Form of Mass/Intensity Lists
555 acetophenone
m/z int.
42 21
61 13
75 36
105 1000
m/z
43
62
76
106
int.
245
26
62
87
m/z
49
63
77
120
int.
19
422
941
479
m/z
50
65
78
121
int.
221 .
31
11
38
m/z
51
73
89
int.
524
13
12
m/z
52
74
91
int.
75
64
22
556 4-aminobiphenyl
m/z int.
51 55
139 65
557 aniline
m/z int.
40 65
51 47
63 59
91 10
558 o-am'sidine
m/z int.
40 22
53 286
65 142
80 915
108 1000
559 aramite
m/z int.
41 606
77 155
163 143
319 270
560 benzanthrone
m/z int.
74 69
101 278
202 762
m/z
63
141
m/z.
41
52
64
92
-------
Appendix A (continued)
Mass Spectra in the Form of Mass/Intensity Lists
563 2,3-benzof luorene
B& Icis. mfz
74 52 81
108 491 187
216 1000 217
943 benzole acid
m/z int. m/z
45 29 50
75 25 76
564 benzyl alcohol
m/z Int. B/Z
40 17 59
61 11 62
75 13 76
89 65 90
108 737 109
565 2-bromochlorobenzene
m/z Int. m/z
49 237 50
76 202 111
566 3-bromochlorobenzene
S& int. g£j
49 201 50
76 197 111
567 4-chloro-2-nitro*niline
Sfjt .intt m/z
49 119 50
63 1000 64
76 127 78
126 766 128
568 5-diloro-o-toluidine
m/z int. m/z
50 115 51
79 140 89
143 313
569 4-chloroaniline
S& int. m/z
41 60 62
91 63 92
129 292
570 3-chloronitrobenzene
SiS. int. m/z
50 619 51
85 101 99
int.
69
75
166
int.
221
81
int.
16
31
18
64
43
|nli
890
961
ink.
834
1000
int.
174
315
152
234
int.
261
152
int.
55
186
int.
189
258
m/z
94
189
•Hz
51
77
mZs
50
63
77
91
mjz.
51
113
i£
S1
113
m/z
51
65
90
142
E£!
52
106
5££
63
99
l£
73
111
int,.
143
90
int.
413
778
int.
155
70
565
125
int.
183
287
int.
174
301
int.
260
192
724
211
int.
257
1000
int.
147
67
int.
144
851
ra/z
95
213
m£z
52
78
m/z
51
64
78
105
m/i
73
190
i&
73
190
&z
52
73
91
172
MZ
53
140
i£z
64
100
S£z
74
113
int.
253
233
int.
45
76
int.
319
12
116
38
int.
158
638
int.r
169
625
int.
531
290
253
915
int.
137
599
int.
135
115
int.
330
266
ffl£z
106
214
m/z
66
105
Silz.
52
65
79
106
mjz
74
192
S£z.
74
192
all
61
74
101
174
s&
77
141
!S£z
65
127
ntfz
75
157
int.
60
60
int..
11
1000
int.
78
75
1000
18
int.
506
809
Int..
509
802
int.
205
105
232
289
int.
420
964
int.
329
1000
int.
1000
424
m/z
107
215
m/z
74
122
m/z
53
74
80
107-
E&
75
194
m/z
75
194
E£z
62
75
114
m/z
78
142
m/z
73
128
m/z
76
159
int.
205
987
int.
53
868
int.
84
35
73
523
int.
1000
193
int.
914
191
int.
394
156
312
int.
134
265
int.
51
81
int.
169
137
66
-------
Appendix A (continued)
Mass Spectra in the Form of Mass/Intensity-Lists
571 o-cresol
tn/z int. m/z int.
50 102 51 181
89 114 90 231
944 p-cresol
m/z int. m/z int.
50 136 51 224
80 145 90 122
572 crotoxyphos
m/z int. m/z int.
40 633 44 448
105 484 109 21
573 2,6-di - t-butyl -p-benzoquinone
m/z int. m/z int.
51 392 53 586
77 376 79 308
135 538 136 240
220 410
574 2,4-diaminotoluene
m/z int. m/z int.
40 70 42 55
67 50 77 147
105 134 106 67
575 1,2-dibromo-3-chloropropone
\Sl2. int. m/z int.
42 38 59 341
77 331 81 43
106 17 119 74
159 204 187 10
945 3,5-dibromo-4-hydroxybenzonitrUe
m/z int. m/z int.
53 148 61 193
170 141 275 489
576 2,6-dichloro-4-nitroaniline
m/z int. m/z tot.
41 206 52 1000
65 137 89 218
133 218 160 401
577 1,3-dichloro-2-propanol
m/z int. m/z int.
40 14 42 55
49 113 50 15
78 11 79 1000
m/z
53
107
m/z
52
107
m/z
67
127
m/z
55
91
149
m/2
51
78
121
g&
51
93
121
m/z
62
277
m/z.
61
90
176
m/z
43
51
80
int.
144
783
int.
106
822
int.
42
1000
int.
325
456
429
int.
76
69
958
int.
104
117
66
int.
222
1000
int.
523
443
431
int.
503
37
25
m/z
77
108
m/z
53
108
m/z
77
166
m/z
57
95
163
s£s
52
93
122
ff/z.
61
95
155
m/z
88
279
m/z.
62
97
178
m/z
44
57
81
int.
358
1000
int.
196
1000
int.
70
180
*
int.
668
322
292
int.
70
63
1000
int.
38
106
635
int.
632
451
int.
828
458
134
int.
22
10
310
m/z
79
m/z
77
m/z
79
193
m/z
65
107
177
B/z
53
94
123
a££
75
97
157
m/z
117
m/z
63
124
206
m/z
47
61
int.
380
int.
420
int.
41
401
int.
416
248
1000
int.
51
224
79
lot.
1000
12
784
int.
137
int.
588
954
378
int.
12
12
m/z
80
m/z
79
m/z
104
194
m/af
67
121
205
m/i
61
104
B/Z
76
105
158
m/z
"Ti TTi
168
m/z
73
126
m/z
58
75
int.
159
int.
308
int.
100
20
int.
927
255
203
int.
91
128
int.
75
67
20
int.
^•^•^-^
152
int.
470
401
int.
15
14
67
-------
Appendix A (continued)
Mass Spectra in the Form of Mass/Intensity Lists
578 2,3-dichloroaniline
l£j int. m/z int.
52 138 61 151
73 130 90 460
163 626 165 101
579 2,3-dichloronitrobenzene
m/z ,int. m/z int.
49 220 50 257
74 976 75 743
110 204 111 303
161 190 163 121
946 2,6-dichlorophenol
SiS. int. m/z int.
49 111 62 160
126 260 162 1000
580 1,2:3,4-diepoxybutane
g£j int.. m/z int.
40 37 41 29
57 155 58 16
581 3,3'-dinethoxybenzidine
!& jntTl m/z int.
65 44 79 222
122 115 158 154
245 152
582 dimethyl sulfone
&£t ,
-------
Appendix A (continued)
Mass Spectra in the Form of Mass/Intensity Lists
586 3,6-dimethylphenanthrene
m/z
76
190
587
m/z
50
76
588
m/z
" /i *j
50
110
589
m/z
42
64
97
590
m/z
41
73
591
m/z
41
160
310
592
m/z
47
141
947
m/z
41
56
73
593
m/z
51
128
170
594
m/z
50
104
int. m/z
113 89
193 191
1 ,4-dinitrobenzene
int. m/z
1000 51
664 92
diphenyldisulfide
int. m/z
153 51
132 154
ethyl methanesulfonate
int. m/z
16 43
22 65
206 109
ethyl eneth i ourea
int. m/z .
46 42
151 102
int.
129
430
int.
131
240
int.
293
191
int.
72
93
579
int.
126
1000
m/z
94
205
m/z
63
122
m/z
65
185
m/z
45
79
111
m/z
45
int,.
179
246
int.
228
166
int.
671
117
int.
208
1000
18
int.
97
m/z
101
206
m/z
64
168
m/z
59
218
m/z
48
80
123
m/z
46
int.
142
1000
int.
218
399
int.
282
418
I**
int.
40
127
15
int.
42
m/z
102
207
m/z
74
m/z
77
m/z
59
81
124
m/z
59
int..
151
159
int.
311
int.
141
int.
19
42
33
int.
14
m/z
189
m/z
75
m/z
109
m/z
63
96
m/z
72
int.
388
int,.
623
int.
1000
int.
23
16
int.
89
ethynylestradiot 3-methyl ether
int. m/z
155 53
115 173
516
hexach I oropropene
int. m/z
131 71
206 143
hexanoic acid
int. m/z
627 42
90 57
412 74
2- isopropylnaphthalene
int. m/z
100 63
216 152
368
isosafrole
int. m/i
110 51
441 131
int.
101
199
int.
333
196
int.
535
102
56
int.
111
133
int.
222
371
m/z
91
174
m/z
106
211
m/z
43
60
87
m/z
76
153
m/z
63
132
int.
157
313
int.
334
631
int.
214
1000
98
int.
157
184
int.
127
107
m/z
115
227
ro/z
108
213
m£z
45
61
m/z
77
154
m/z
77
135
int.
143
1000
int.
200
1000
int.
186
66
int.
129
114
int.
277
129
m/z
147
228
m/z
117
215
m/z
46
69
m/z
115
155
m/z
78
161
int.
226
149
int.
329
623
int.
19
21
int.
147
1000
int.
208
250
m/z
159
242
m/z
119
217
m/z
55
70
m/z
127
156
m/z
103
162
int.
132
153
int.
320
186
int.
128
20
int.
131
139
int.
355
1000
69
-------
------- |