United States
Environmental Protection
Agency
Environmental Monitoring and
Support Laboratory
Cincinnati OH 45268
Research and Development
EPA/600/S4-86/001 Jan. 1986
x°/EPA Project Summary
Evaluation of Methods for
Hazardous Chemicals Listed in
Appendix D to 40 CFR 122
(Table V)
S. V. Lucas, M. Cooke, and T. F. Cole
This study involved method develop-
ment for several compounds that had
not been tested by existing U.S. EPA
Methods: semivolatiles volatiles
(6 compounds), purgeables (3 com-
pounds), volatile amines (6 com-
pounds), and alcohol amines (2 com-
pounds). These compounds are on a list
of 75 organic compounds in Table V of
Appendix D to 40 CFR 122. Of those
75 compounds, 24 had not been tested
by an existing EPA method for analysis
in water and wastewater. The present
work reports on efforts to demonstrate
the analytical performance of 17 of
those 24 compounds plus an additional
five compounds not included in Table V
of Appendix D by applying existing 600-
series methods with appropriate modi-
fications. In each case, a test analyte set
for a given method/approach consisted
of essentially all of the Appendix D
Table V compounds belonging to that
compound class. The approach was to
demonstrate performance separately in
the areas: (1) chromatography -using
fused silica capillary columns whenever
possible and including the evaluation of
cold, on-column injection whenever
necessary, (2) modified extraction and
concentration techniques, and (3) mod-
ified cleanup techniques. In cases
where all of these areas gave appropri-
ate results, an integrated method was
tested for accuracy and precision.
For the semivolatile compounds (6 of
the 17), two compounds (benzonitrile
and quinoline) gave excellent recovery
and precision through extraction and
cleanup, three other compounds (ke-
pone, strychnine and dichlone) gave 50
to 80 percent recovery, and one com-
pound (trichlorfon) was not stable in
aqueous systems at neutral pH.
For the purgeable compounds (3 of
17), one analyte (propylene oxide) gave
marginally acceptable precision results,
with the observed deficiency appar-
ently due to hydrolysis during the
purge-and-trap desorption step. The
other two analytes gave unacceptable
results but for different reasons: ally!
alcohol was purged with efficiency only
15 percent at 85°C and also gave unac-
ceptable GC peak tailing, resulting in a
relatively high estimated detection
limit of 70 |ig/L. Although methyl mer-
captan also exhibited some tendency
toward decomposition on the trap, the
principal difficulty is its elution early in
the chromatogram where baseline dis-
turbances and methanol elution occur.
A "Hall detector" in the sulfur detection
mode is recommended for analysis of
methyl mercaptan by the room temper-
ature purge-trap-desorb approach.
For the volatile amines (6 of the 17), a
special GC packing material was pre-
pared and demonstrated to be effec-
tive. However, all efforts to develop a
purge-trap-desorb sample workup pro-
cedure were unsuccessful. For the alco-
hol amines (2 of the 17), none of the gas
chromatography approaches tried pro-
vided performance adequate to justify
further method development.
This Project Summary was devel-
oped by EPA's Environmental Monitor-
ing and Support Laboratory, Cincinnati,
-------
OH, to announce key findings of the re-
search project that is fully documented
in a separate report of the same title
(see Project Report ordering informa-
tion at back).
Introduction
The objective of this research was to
evaluate analytical methods for haz-
ardous chemicals listed in Appendix D
to 40 CFR 122 (Table V). This listing con-
tains 75 organic chemicals that must be
analyzed if they are expected to be
present in existing discharges. Stand-
ard analytical methods have been de-
veloped and validated by the EPA for
most of these 75 Appendix D/Table V
compounds. The 24 untested com-
pounds are listed in Table 1. Seven of
these 24 untested compounds were of
chemical classes that were beyond the
scope of this work, and, therefore they
were eliminated by the Project Officer
from method evaluation. Thus, the work
reported here focused on 17 of the
untested compounds thought to be
amenable to gas chromatography (GC).
A major objective of this work was to
provide a minimum number of methods
to cover a maximum number of Ap-
pendix D/Table V compounds. This
would minimize the effort required by
the analyst. Accordingly, the Ap-
pendix D/Table V chemicals were di-
vided into six chemical classes, each of
which contained at least one of the
untested compounds. These chemical
classes were: organophosphorous
compounds, neutral nitrogen com-
pounds, chlorinated pesticides, ex-
tractable semivolatile bases, volatile
compounds, volatile amines, and alco-
hol amines. The chemical class of each
untested compound is identified in
Table 1. In this work, methods were
evaluated for all or nearly all of the Ap-
pendix D/Table V compounds of each
class to ensure that method modifica-
tions which enhanced performance for
a high-interest analyte did not detract
from the method performance already
in place for the other compounds in the
class. In addition, the volatile com-
pounds class was augmented by an ad-
ditional five compounds which were not
in the Appendix D/Table V listing but
were of interest to the EPA Project Offi-
cer. These compounds were acetone,
methyl ethyl ketone, methyl isobutyl ke-
tone, methyl butyl ketone, and dioxane.
This report addresses a total of 22 com-
pounds which are broadly sub-
classified into three sets: semivolatile
(extractable) compounds, volatile
(purgeable) compounds, and amines
(including alcohol amines).
Experimental Design
The experimental design for each of
the three compound classes incorpo-
rated independent evaluation of four as-
pects of a method: chromatographic
separation, injection conditions, sample
workup, and cleanup procedures. A
main feature of the chromatographic
separation evaluation for semivolatile
compounds was to test both polar and
nonpolar fused silica capillary columns.
Injection conditions tested for the
semivolatile group were evaporator
cavity (split/splitless) injection at vari-
ous temperatures for all compound sets
and cold, on-column injection for se-
lected compound sets. Sample workup
for semivolatile compounds involved
liquid-liquid extraction and extract con-
centration, while cleanup procedures
emphasized Florisil column techniques
using solvent systems already in use in
EPA cleanup methods. When reason-
able results were obtained in each of
these areas, the precision and accuracy
of the integrated method was tested.
The purge-and-trap analysis condi-
tions were essentially those of Method
5030 employing room temperature
purging with the three-component trap
(Tenax, silica gel and activated carbon)
for nonpolar compounds and 85°C
purging with the all-Tenax trap for polar
compounds. Three GC column packings
were tested Porapak-QS, 10 percent
Carbowax 20M on Supelcoport, and
1 percent SP1000 on Carbopack B, and
the latter one was selected for the re-
covery and precision studies. Reagent
water was used as the matrix in all spike
recovery experiments, and a Tekmar
LSC-2 purge-and-trap apparatus was
used to generate the data.
Studies with the amine analyte set
were restricted to the establishment of
an adequate column packing material,
feasibility studies on the purge-and-trap
sample processing approach, and an in-
vestigation of the applicability of auto-
mated heated headspace sampling with
capillary chromatography using a
Perkin-Elmer HS-100 automated
headspace sampling unit.
Results and Discussion
Organophosphorous Com-
pounds
Trichlorfon is the only organophos-
phorous compound listed in Table 1.
Appendix D to 40 CFR 122 (Table V) con-
tains an additional 11 organophospho-
rous compounds: chlorpyriphos,
coumaphos, diazinon, disulfoton,
ethion, guthion, malathion, methyl
parathion, mevinphos, naled, and
parathion. GC studies with all 12 com-
pounds showed that trichlorfon was es-
sentially quantitatively decomposed
upon splitless, evaporator cavity injec-
tion above 250°C. In addition, mevin-
phos decomposed significantly and
naled decomposed slightly under those
injection conditions. Therefore, cold on-
column injection was used for all subse-
quent work. Studies using separatory
funnel shakeout, reverse phase extrac-
tion, and KD concentration with the two
most labile compounds (mevinphos
and trichlorfon) showed that trichlorfon
decomposed, essentially quantitatively,
in pH 7-buffered reagent water, but that
it survived KD concentration in a variety
of solvents. Once it was shown that the
only Table 1 organophosphorous com-
pound, trichlorfon, was not stable in
water, experimental work on the re-
maining 11 compounds was termi-
nated.
Neutral Nitrogen Compounds
Of 13 neutral nitrogen compounds on
the Table V list of Appendix D 40 CFR
122, benzonitrile was the only untested
(Table 1) compound. The other 12 com-
pounds are: diuron, dichlobenil, carbo-
furan, mexacarbate, carbaryl, methio-
carb, and all isomers of nitrotoluene
and dinitrobenzene. The chromato-
graphic performance of all 13 com-
pounds was tested using 30 meter SPB-
5 and Carbowax 20M fused silica
capillary columns. The high polarity and
high molecular weight pesticides failed
to elute from the Carbowax 20M
column. Subsequent work with the
SPB-5 column using GC-MS demon-
strated that diuron decomposed quanti-
tatively in the evaporator cavity injector
at temperatures between 250 and
300°C, and that carbofuran, mexacar-
bate, carbaryl and methiocarb partially
decomposed (up to 50 percent at 300°C)
over that range. Since the untested
compound benzonitrile performed well
under these injection conditions, testing
with cold, on-column injection was not
conducted. The extraction efficiency of
benzonitrile from reagent water aver-
aged 103 ±8 percent using methylene
chloride. Extraction efficiencies for the
other 12 compounds were not tested
since they are all listed in current EPA
methods. A Florisil column cleanup pro-
cedure was evaluated for all com-
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pounds except diuron. Nitrotoluenes
were recovered in the 20 percent diethyl
ether in hexane elution fraction (frac-
tion 1). Carbofuran and carbaryl were
recovered in the 15 percent acetone in
hexane fraction (fraction 3). The other
compounds were recovered in the
6 percent acetone in hexane fraction
(fraction 2). Recoveries of all com-
pounds were 79 percent or greater ex-
cept for mexacarbate and methiocarb.
They were recovered at about 35 per-
cent. Four replicate analyses of reagent
water spiked at the 25 (tg/L level with
the 12 compounds (diuron omitted)
were carried through the extraction,
concentration, and cleanup sequence.
They were analyzed using a nitrogen
specific detector to generate accuracy
and precision data. The results showed
recoveries between 72 and 80 percent
with relative standard deviation (BSD)
values between 10 and 15 percent for
benzonitrile, and three nitrotoluenes, di-
clobenil and 1,2-dinitrobenzene. The re-
coveries for 1,3-dinitrobenzene and 1,4-
dinitrobenzene were 72 ± 23 and
64 ± 12 percent, respectively. The re-
covery and precision data obtained for
carbofuran, mexacarbate, carbaryl and
methiocarb were 120 ± 17, 98 ± 25,
144 ±20 and 10 ± 7, respectively. Un-
doubtedly, the observed splitless injec-
tion decomposition for these four pesti-
cides accounts for a large measure of
the variability in these results. The low
(10 percent) recovery of methiocarb
could not be attributed to a specific
cause.
In summary, benzonitrile can be de-
termined using methylene chloride ex-
traction, Florisil column cleanup, and
fused silica, capillary column GC analy-
sis with nitrogen-specific detection. The
overall recoveries obtained for the ni-
trotoluenes, dinitrobenzenes and
dichlobenil were generally acceptable
at 70 to 80 percent, but somewhat er-
ratic results for carbofuran, mexacar-
bate, carbaryl and methiocarb prevent
making any definitive method perform-
ance conclusions on those four com-
pounds.
Chlorinated Pesticides
The two untested Table 1 compounds
in this group were diclone and kepone.
Methoxychlor and captan, which are
also in Table V of Appendix D/40 CFR
122, were also included in the study. Of
the four compounds, only diclone
eluted from the Carbowax 20M fused
silica capillary column. Excellent chro-
matographic performance was ob-
Table 1. Untested Compounds from Table V of Appendix D to 40 CFR 722
Compound
Chemical Class
Allyl alcohol
Bemonitrile
Butylamine
Dichlone
2,2-Dichloropropionic acid
Diethylamine
Diquat
Ethanolamine
Isopropanolamine
Kepone
Methyl mercaptan
Ethylamine
Methylamine
Naphthenic acid
Phenol sulfonate
Phosgene
Propargite
Propylene oxide
Pyrethrins
Quinoline
Strychnine
Trichlorfon
Trimethylamine
Triethylamine
Volatile compound
Neutral nitrogen compound
Amine
Chlorinated pesticide
(Eliminated)
Amine
lEIiminated)
Amine
Amine
Chlorinated pesticide
Volatile compound
Amine
Amine
(Eliminated)
(Eliminated)
(Eliminated)
(Eliminated)
Volatile compound
(Eliminated)
Extractable semivolatile base
Extractable semivolatile base
Organophosphorous compound
Amine
Amine
tained for all four compounds using the
SPB-5 nonpolar fused silica capillary
column. Captan, however, apparently
decomposed in the 300°C evaporator
cavity, splitless injector. Since captan
was not a high-priority. Table 1 analyte,
and since this partial decomposition did
not seem to have any effect on analysis
precision, cold, on-column injection
was not tested for this analyte set.
Neutral pH extraction of aqueous
spiked samples with methylene chlo-
ride was shown to be an effective ex-
traction approach with recovery rang-
ing from 76 to 92 percent and precision
ranging from 7 to 12% BSD. The elution
scheme using Florisil column cleanup
was modified by the addition of 100 per-
cent ethyl ether and 6 percent acetone
in ethyl ether elutions to provide recov-
eries of the four analytes.
The integrated method including
methylene chloride extraction, KD con-
centration, Florisil column cleanup and
GC-ECD analysis using a nonpolar
fused silica capillary column was tested
with four 1-L reagent water replicates
spiked with 25 \t.g of each of the four
analytes. All applicable Florisil column
eluates were pooled before analysis.
The average percent recoveries, and
standard deviations obtained were di-
clone, 48 ± 7 percent, captan 71 ± 13
percent, kepone 74 ± 5 percent, and
methoxychlor 92 ± 7 percent. The poor
recovery for diclone is probably due to
losses at the Florisil column cleanup
step and/or KD distillation of the ethyl
ether-containing Florisil elution solvent.
Except for dichlone, which is an
untested Table 1 compound, analysis
method performance for the chlori-
nated pesticides was judged accept-
able.
Extractable Semivolatile Bases
This group of three compounds con-
sisted of two high-interest compounds
from Table 1 (quinoline and strychnine)
plus aniline. Since strychnine did not
elute from the polar, Carbowax 20M
column the SPB-5 (Supelco) nonpolar
fused silica capillary column was used
for all of the studies performed on this
group. Aqueous extraction studies with
methylene chloride at both neutral and
basic pH, both with and without acidic
pre-extraction and/or salting out
(sodium chloride at 200 g/L), gave quan-
titative recovery of aniline and quino-
line but only 46 to 58 percent recovery
of strychnine. Extraction using two sol-
vent systems, 15 percent hexane in
methylene chloride, and methyl t-butyl
ether, gave similar results except that
the strychnine recoveries were 38 and
10 percent, respectively. A check of the
KD concentration procedure indicated
that for methylene chloride, the poor
strychnine extraction recovery was
probably due to losses at that stage.
Similar results were obtained for diethyl
ether, but essentially quantitative KD
concentration recovery was obtained
for strychnine with methyl t-butyl ether
solvent. Quantitative recovery through
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the K-D step was also obtained for ani-
line and quinoline with both solvents.
Since suitable extraction conditions
could not be identified for strychnine,
further work to test cleanup procedures
and an integrated method for the ex-
tractable semivolatile bases was not
conducted.
Volatile Compounds
Of 17 volatile compounds tested, only
three are high-interest. Table 1 com-
pounds: methyl mercaptan, propylene
oxide and allyl alcohol. Fourteen other
compounds were included in the
volatile set. Of those 14 compounds,
9 compounds were from Table V of Ap-
pendix D 40 CFR 122, and 6 compounds
were specified by EPA. This 17-
compound analyte set was divided into
polar and nonpolar sets for which an
85°C and ambient temperature, respec-
tively, purge-trap-desorb approach was
employed. These analyte sets are
shown in Table 2. The traps used were
those of Methods 8030 (85°C purge) and
8010 (ambient temperature purge) with
the purge-trap-desorb conditions as
specified in Method 5030. A Tekmar
LSC-2 liquid sample concentrator inter-
faced to a GC with flame ionization de-
tector was used for all sample analyses.
Three GC column packings were
tested in this work: Porapak OS, 10 per-
cent Carbowax 20M on Supelcoport 80/
100, and 1 percent SP1000 on Carbo-
pack B 60/80. The latter packing, in a
6 foot, 2 mm I.D. glass column, pro-
vided the best performance for all
analytes and was used to produce the
data reported here. Neither of the other
two columns performed adequately for
recommendation as a backup column in
these analyses.
The most volatile analytes were
checked for trap breakthrough. As ex-
pected, none of the nonpolar analyte
broke through the Method 8010 trap at
less than 1600 mL purge volume. For
the polar analytes, only acetone and
propylene oxide, with breakthrough
volumes of 560 and 400 ml, respec-
tively, for 1.0 |xg trap loadings, ap-
proached the 300 ml purge volume of
Method 5030.
Purging and desorption efficiencies
were separately determined. For the
nonpolar analytes, all but methyl mer-
captan and propylene oxide were quan-
titatively purged and desorbed. Propy-
lene oxide purged with only about
25 percent efficiency, and about two
thirds of the purged amount apparently
decomposed during desorption giving
an overall recovery of 9 percent. For
methyl mercaptan, 70 percent purging
efficiency was found, but a 50 percent
loss on desorption gave a 35 percent
overall recovery. For the polar analytes,
only the ketones approached quantita-
tive purge/desorb recoveries (87 to 100
percent). Lower overall recoveries for
the acetates was entirely attributable to
desorption losses of 50, 20 and 35 per-
cent for the vinyl, butyl and amyl ac-
etates, respectively. Epichlorohydrin
was also found to purge essentially
quantitatively but experienced about
80 percent loss on desorption. The two
remaining analytes, allyl alcohol and
dioxane, were desorbed with about
90 percent recovery but were purged
with only about 15 percent efficiency.
Replicate analyses of low-level spiked
reagent water samples were performed
to estimate the detection limits for all
analytes except methyl mercaptan, and
the results are shown in Table 2. Some
Table 2. Estimated Detection Limits for Volatile Analyte Sets
Polar Compounds
(85°C Purge)
allyl alcohol1*'
propylene oxide1*1
epichlorohydrin
vinyl acetate
butyl acetate
amyl acetate
acetonelc>
methyl ethyl ketonelc>
methyl isobutyl ketone<0>
methyl butyl ketonelc>
dioxanelcl
Estimated
Detection
Limit,
W/L
70
5
10
2
1
2
4
0.3
0.3
0.6
10
Nonpolar Compounds
(Room Temperature Purge)
methyl mercaptanla>
propylene oxide1"1
allyl chloride
isoprene
cyclohexane
o-xylene
ethyl etherA high-interest. Table 1 compound. Note that propylene oxide is included in both analyte
sets.
"''Not determined, see discussion in text.
M Compound not listed in Table V of Appendix D to 40 CFR 122.
4
analytical problems were encountered
with all three of the high-interest ana-
lytes, propylene oxide, methyl mercap-
tan and allyl alcohol. Propylene oxide
can be analyzed by either the room tem-
perature or 85°C purge-and-trap ap-
proach. However, the propylene oxide
data clearly indicate that this compound
partially decomposes during trap de-
sorption, and the result is that variable
precision and accuracy might be ex-
pected without further method im-
provements. Indeed, most of the prob-
lems associated with the
purge-and-trap analyte sets were
shown to be associated with decompo-
sition, probably by hydrolysis, during
trap desorption. Two additional prob-
lems were encountered with methyl
mercaptan: (1) FID sensitivity was low,
as expected, and (2) near coelution with
methanol, significantly reduced its re-
producibility. Both of these problems
could be eliminated with a sulfur-
specific detector. In the case of allyl
alcohol, the estimated detection limit of
70 n-g/L was due partially to the very low
purging efficiency (about 15 percent) at
85°C but primarily to the extreme GC
peak tailing on the 1 percent SP1000/
Carbopack B column.
Volatile Amines and Alcohol
Amines
Five of the six amines tested are high-
interest, Table 1 compounds: trimethy-
lamine, ethylamine, diethylamine, tri-
ethylamine, and butylamine. The sixth
amine in the set was methylamine. The
two alcohol amines tested were
ethanolamine and isopropanolamine,
also high-interest. Table 1 compounds.
Chromatographic characteristics of
the amines were investigated using
commercially available fused silica cap-
illary columns, Carbowax 20M and DB-
5, and column packings, Porapak QS
and 1 percent SPIOOO/Carbopack B, plus
a custom-made packing based on Car-
bopack B treated with KOH (0.3 percent)
and then coated with 4.8 percent Car-
bowax 20M. The later column was the
only one which gave adequate perform-
ance for all six amines.
Volatile amine sample workup stud-
ies were limited to feasibility investiga-
tions of purge-and-trap-based and
heated headspace sampling ap-
proaches. None of the three traps tested
performed adequately. The Method
8010 trap and an activated carbon trap
prevented breakthrough but gave poor
or no desorption recoveries. The
Method 8030 trap gave good desorption
-------
recoveries but exhibited breakthrough
for methylamine, ethylamine, and
trimethylamine. Since an adequate trap
was not available, purging efficiency
studies were not performed. Automated
heated headspace sampling performed
well for tertiary amines but very poorly
for primary amines, apparently due to
adsorptive problems with metallic com-
ponents of the autosampler. For the al-
cohol amines, none of the chromato-
graphic approaches tested gave
adequate chromatographic perform-
ance, and, without a determinative tech-
nique for these compounds, no further
work was possible.
Conclusions and Recommenda-
tions
The low method development suc-
cess rate for the 17 untested, Table 1
compounds tested reflects the multi-
plicity of their chemical characteristics
which prevent analysis using ordinary
approaches. Only six of the 17 untested
Table 1 compounds (benzonitrile,
quinoline, kepone, strychnine, dichlone
and propylene oxide) gave acceptable
or marginally acceptable results. One
compound, trichlorfon, is not stable in
water, and no further method develop-
ment work for aqueous matrices should
be pursued. Further method develop-
ment for methyl mercaptan should in-
clude a purge-and-trap approach with
Hall electrolytic conductivity/sulfur
mode detection. If the chromatographic
tailing problem can be solved, ally! alco-
hol may be effectively analyzed with an
85°C purge-and-trap approach even
though it has only a 15 percent purging
efficiency. In general, loss of labile ana-
lytes during trap desorption is a prob-
lem that should be addressed to im-
prove the performance of many of the
volatile analytes. Although good chro-
matography was achieved for the
volatile amines, the method currently is
limited to direct aqueous injection. Fur-
ther work on the six volatile amines
should include pre-analysis concentra-
tion method development and investi-
gation of alternate determinative tech-
niques such as ion chromatography,
especially for the alcohol amines (2 of
the 17 high-interest compounds).
S. V. Lucas. M. Cooke, and T. F. Cole are with Battelle Laboratories, Columbus
Division. Columbus. OH 43201 -2693.
James Longbottom is the EPA Project Officer (see below).
The complete report, entitled "Evaluation of Methods for Hazardous Chemicals
Listed in Appendix D to 40 CFR 122 (Table V)," (Order No. PB 86-136 520/A S;
Cost: $16.95, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Environmental Monitoring and Support Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
U. S. GOVERNMENT PRINTING OFFICE:1986/646-l 16/20758
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Environmental Protection
Agency
Center for Environmental Research
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