-13-

Table I (cont'd)

Purging
Efficiency
Purging - Modified
(b) Efficiency Method
Compound RRT (percent) (percent)
1,4-dichlorobutane (IS) 1.312 74
toluene 1.341 no data
chlorobenzene 1.489 89
ethylbenzene 1.814 no data
acrolein unknown 12 74 e)
acrylenitrile unknown no data

(a)

(b)

(c)

(d)

({e)

These data were obtained under the following conditions:
GC column - stainless steel, 8 ft. long x 0.1 in. I.D.
packed with Carbopack C (60/80 mesh), coated with 0.2%
Carbowax 1500; preceeded by al ft. long x 0.1 in. I.D.
column packed with Chromosorb W coated with 3% Carbowax
1500; carriez flow - 40 ml/min.; oven temperature -
initial 60°C held for 3 min., programmed 8°C/min. to
160°C and held until all compounds eluted. The purge
and trap system used was constructed by EPA. Under
optimized conditions, commercial systems will provide
equivalent results.

Retention times relative to 2-bromo-l-chloropropane
with an absolute retention time of 829 seconds.

No measurable recovery using standard purging and trap-
ping conditions. Under medified conditions, i.e.,
purging at 10 ml/min. for 12 min., recovery is 100%.

Bis-chloromethyl ether has a very short half-life in
water and is not likely to be detected in water.

Recovery 12% under standard purging ccnditions, i.e.,
room temperature, 30% at 55°C, and 74% at 95°C.


TM -

fable Iv. Base-neutral Extractables
revi Limit of
(hexachloro- Detection Characteristic

Compound Nama benzene) (ng) EI_ ions (Rel. Int.)
1,3-dichlorobenzene 0.35 40 146(100), 148(64), 113(12)
1,4-dichlorobenzene 0.36 40 146 (100) ,- 148(64), 113(21)
hexachloroethane 0.38 40 117(100), 199(61), 201(99)
1,2-dichlorobenzene 0.39 40 146(100), 1409(64), 113(11)
bis (2-chloroisopropyl)

ether 0.47 40 45(100), 77(19), 79(12)
hexachlorobutadlene 0.55 40 225(100, 223(63), 227(65)
1,2,4-trichlorobenzene 0,55 - 40 74(100), 109(80), 145(52)
naphthalene 0.57 40 128(100), 127(10), 129(11)
bis (2-chloroethy1) ether 0.61 40 93(100), 63(99), 95(31)
hexachlorocyclopentadiene 0.64 40 237(100), 235(63), 272 (12)
nitrobenzene 0.64 40 77(100), 123(50), 65(15)
bis (2-chloroethoxy) methane 0.68 40 93(100), 95(32), 123(21)
2-chloron aphthalene 0.76 40 162(100), 164(32), 127(31)
acenaphthylene 0.83 40 152(100), 153(16), 151(17)
acenaphthene 0.86 40 154(100), 153(95), 152(53)
isophorone 0.87 40 82(100), 95(14), 138(18) ©
fluorene 0.91 40 166(100), 165(80), 167(14)
2,6-dinitrotoluene 0.93 40 165(100), 63(72), 121(23)
1,2-diphenylhydrazine 0.96 40* 77(100), 93(58), 105(28)
2,4-dinitrotoluene 0.98 40 165(100), 63(72), 121(23)
N-nitrosodiphenylamine 0.99 40* 169(100), 168(71), 167(50)
hexachlorobenzene 1.00 40 284 (100), 142(30), 249(24)
4-bromophenyl phenyl ether 1.01 40 248(100), 250(99), 141(45)
phenanthrene 1.09 40 178(100), 179(16), 176(15)
anthracene 1,09 40 178(100), 179(16), 176(15)
dimethylphthalate 1.10 40 163(100), 164(10), 194(11)
diethylphthalate 1.15 40 149(100), 178(25), 150(10)
fluoranthene 1,23 “40 202(100), 101(23), 100(14)
pyrene 1.30 40 202 (100), 101(26), 100(17)
di-n-butylphthalate 1.31 40 149(100),.150(27), 104(10)
benzidine 1.38 40* 184 (100).,92(24), 185(13)
butyl benzylphthalate 1.46 40 149(100), 91)50)

CI ions.
(Methane)

146, 148,
146, 148,
199, 201,
146, 148,

150
150
203
150

77, 135, 137

223, 225,
181, 183,
129, 157,

227
209
169

63, 107, 109

235, 237,
124, 152,

239
164

65, 107, 137

163,
152,
154,
139,
166,
183,
185,
193,
169,
284,
249,
178,
178,
151,
177,
203,
203,
149,

185,
149,

191,
153,
155,
167,
167,
211,
213,
211,
170,
206,
251,
179,
179,
163,
223,
231,
231,
205,

213,
299,

203
181
183
178
195
223
225
223
198
288
277
207
207
164
251
243
243
279

225
327


- 30 -
Standards for the priority pollutants may be obtained
from the sources listed in Appendix II. Those compounds

Marked with an asterisk have not yet been received by the

Athens laboratory.

In order to minimize unnecessary GC-MS analysis of blanks,
the extract may be run on a FID-GC equipped with appropriate
$P2250 and Tenax GC columns. If no peaks are seen of intensi-
ties equal to or greater than the deuterated anthracene internal
standard, then it is not necessary to do a GC-MS analysis. I£
such peaks are seen, then the blank must be sent for full

priority pollutant analysis.

The contractor will look for all priority pollutants to
the limit of 10 ug/L except in those cases listed in Tables Iv-v
in which limits of detection are too high for analysis at this

level.

Reporting of Data

All concentrations should be reported in ranges--10 ppb,
100 ppb, and greater than 100 ppb. Report.concentrations for
pesticides as prescribed in the Federal Register Method. The
relative response ratios from MS analysis should be included

when reporting data.

All GC-MS data is to be saved on 9-track magnetic tape
and sent to the Athens Environmental Research Laboratory for

storage and later evaluation. The tape format is:


- 39 -

Table VI. ELUTION ORDER OF MOST OF THE SEMIVOLATILE
PRIORITY POLLUTANTS ON 18 SP22507 (continued)

=<. - Compound rer? rs
bis (2~ethylhexy1) phthalate 1.50
benzo (a) anthracene , ; 1.54
benzo (b) fluoranthene 1.66
benzo (k) fluoranthene 1.66
benzo (a) pyrene 1.73
indeno (1,2 ,3-cd) pyrene 2.07
dibenzo(a,h) anthracene 2. 12t
benzo (ghi} perylene 2.12%

1% SP~2250 on 100/120 mesh Supelcoport in a6’ x 2m id
“glass colum; He @ 30ml/min; Program: 50° for 4 min,
then 8°/min to 260° and hold for 15 min.

Relative to hexachlorobenzene at 19.4 min.

40ng gives 5-90% response on FID unless otherwise noted.
200ng required to obtain 5-90% response on FID.

2 ug required.

40 ug xecuired.


-7-

Gas Chromatographic Parameters

Column - Stainless steel, 8 ft. long x 1/8 in. O.D.
(0.09 to 0.105 in. I.D.) packed with Carbopack C
(60/80 mesh) coated with 0.2% Carbowax 1500, pre-
ceded by al ft. x 1/8 in. O.D. (0.09 to 0.105 in.
I.D.) packed with Chromosorb-W coated with 3%
Carbowax 1500.

Carrier gas - Helium at 33 ml/min.

Oven temperature - Room temperature during trap desorp-
tion, then rapidly heat to 60°C, hold at 60°C for four min-
utes, then program to 170°C at 8°/minute. Hold at 170°C for

12 minutes or until all compounds have eluted.

Mass Spectrometer Parameters

Data system - System Industries System 150
Separator - glass jet

Electron energy - 70 ev

Emission current - 500 ua

Ion energy = 6 volts

Lens voltage - (-)100 volts

Extractor voltage - 8 volts

Mass range - 20-27, 33-260 amu
Integration time/amu - 17 milliseconds

Samples/amu - 1

Gas Chromatographic Column Conditioning Precedure -
Attach the Carbowax 1500-Chromosorb end of the column to the

inlet system of the gas chromatograph. Do not, at this time,


-67-

Cyanide (Total)

Container - Use new cne-liter plastic bottles that will
Not contaminate the sample. Wash the battles and caps with

hot water and thoroughly rinse with tap water and blank
water.

Collect a 1-liter sample.

Pretreatment and Preservation - Oxidizing agents
such as chlorine decompose many cyanides. Therefore, at
time of collection, samples must be treated to eliminate
such agents. Test a drop of the sample at the time of
collection with potassium jodide-starch test paper
(KI-starch paper); a blue color indicates the need for
treatment. Add ascrobic acid, 2 few crystals at a time,
until a drop of the sample produces no color on the indicator
paper. Then add an additional 0.6 g of ascorbic acid for
each liter af sample volume. Then add 2 ml of 10 N sadium
hydroxide per liter of sample (pH > 12).

Seal the sample bottle and placa in an tnsulated chest
and ice (4°C). Seal the chest and ship to the analytical
Jaboratory. Maintain at 4°C during transport and storages
keep out of direct light prior to analysis.

Phenols

Container - Use new one-liter glass bottles. Wash the bottle
and Teflen cap Tiner with hot water and thercughly rinse with tap
water and blank water.

* Callect 2 l-liter sample.

Preservation - At the time cf collection, acidify the sample
by addition of phospheric acid er sulfuric to pH 4. Note volume
of acid added on sample tag. Seal bottle, placa in insulatad
chest and ica (4°C). Seal chest and‘ship to analytical ;
Jaboratory. Maintain at 4*C during transport and storage. Keep
out of direct light prior ts analysis.


4.

- 49 -

Cyanides

Sample Preparation

All samples are to be distilled prior to determination for
total cyanides. The distillation procedure given on page 43
of “Methods for Chemical Analysis of Water and Wastes, (1974)"

(Reference 7) is to be followed.

Sample Procedure

The procedure for total cyanides as given on pages 43-48
of "Methods for Chemical Analysis of Water and Wastes, (1974)"

(Reference 7) is to be followed.
Quality Assurance

a) Initially, demonstrate quantitative. recovery with
each distillation-digestion apparatus by comparing
distilled standards to non-distilled standards.
Each day, distill at least one standard to confirm
distillation efficiency and purity of reagents.

b) At least 15% of the cyanide analysis will consist
of duplicate and spiked samples. Quality control
limits are to be established ane confirmed as described
in Chapter 6 of the "Analytical Quality Control

Handbook" (Reference 9).

Reporting of Data
Report cyanide concentrations as follows: Less than

1.0 mg/l, nearest 0.01 mg; 1.0 mg/l and above, two significant

figures.


4.

- 47 -

For the determination of selenium the procedure given

for industrial effluents ("Atomic Absorption Newsletter,”

Vol. 14, page 109 [1975]) (Reference 8) should be followed.

Arsenic should be determined in the same manner (using the

nickel nitrate matrix) with an optimum charring temperature

of approximately 1300°c.

The analysis of zinc by flameless AA is difficult because

of environmental contamination. The analyst must take pre-

caution to provide a clean work area to minimize this problem.

e)

Mercury analyses - The cold vapor technique as
described in "Methods for Chemical Analysis of' Water
and Wastes, (1974)", page 118 (Reference 7) is to

be followed.

Quality Assurance

a)

b)

To verify that the instrument is operating correctly
within the expected performance limits, an appropriate
standard should be included between every ten samples.
Spiked aliquots shall be analyzed with a frequency

of 15% cf the sample load for each metal determined
by flame AA. If the recovery is not within +10% of
the expected value the sample should be analyzed by
method ef standard addition. (The spike should be
added to the aliquot prior to sample preparation.)

The amount added should increase the absorbance by
not less than 0.01 units where the absorhance in the
unspiked aliquot was less than 0.1, and not more than

0.1 when the absorbance in the unspiked aliquot was

0.1 or greater.


- 53 -
APPENDIX I

General Information

Emulsions

Limited work with several categories of industrial effluents
covered by this study (tanneries, petroleum, soap and detergent,
steam electric, pesticide) show that emulsions of widely differing
frustration factors are often encountered in the extraction pro-
cedure. Samples that emulsify at basic pH usually also emulsify
at acid pH. There are two equally acceptable alternatives avail-
able for the purposes of this protocol: break the emulsion or start
ever with fresh sample and use a continuous extractor, to prevent

the formation of emulsions.

By the 85% solvent recovery criteria, no way was found to break
the emulsion formed on extraction of untreated tannery wastes. A
soap and detergent sample was also very difficult. The use of a
continuous heavier-than-water liquid extractor allowed the extraction
to take place with no difficulties and very little labor. However,
two days time is required. Comparison of samples from four industries-
petroleum, tannery, pesticide, and soap and detergent--by both shake-
out and continuous extraction using wastes spiked with priority pollu-
tants indicate that the two techniques are comparable. For some
individual cases one technique is better than the other but no clear
pattern emerges. Therefore, if desired, a continuous extraction.
technique may be used in place of separatory funnel extraction for

all samples as well as those for which it is absolutely necessary

because of intractable emulsions.


-57 -
Appendix If

Possible Sources for Some Priority Pollutant Standards

(Continued)
Source of

Compound Standard?
Endosulfan and metabolites
a-endosulfan HERL 23220
B-endosulfan HERL #3200
endosulfan sulfate NI p. 45
Endrin and metabolites
endrin HERL #3260
endrin aldehyde NI p. 147
ethylbenzene Bp. 161
fluoranthene AN p. 118
Haloethers (other than those listed elsewhere)
4-chlorophenyl phenyl ether (p-chloro- .

diphenyl ether) RFR p. 6*
4-bromophenyl phenyl ether ICN p. 37
bis (2~chloroisopropyl) ether PB
bis(2-chloroethoxy) methane PB p. 62
Halomethanes (other than those listed elsewhere)
methylene chloride (dichloromethane) PB p. 276
methyl chloride (chloromethane) PB p. 277
methyl bormide (bromomethane) PB p. 276
bromoform (tribromomethane) PB p. 73
dichlorobromomethaneé cO p. 16
trichlorofluoromethane PB p. 358
dichlorodifluoromethane PB p. 142
chloredibromomethane CO p. 27
Heptachlor and metabolites
heptachlor HERL #3860
heptachlor epoxide HERL 23880
hexachlorobutadiene AL p. 416
Hexachlorobyclohexane (all isomers)
a-BEC HERL #620
8-BHC . HERL 7640
y-BHC (lindane) HERL 3680
6-BEC HERL 2660


- 45 -
Table VIII
Methods for Chemical

Analysis of Water and
Element Wastes, 1974* Comments

Be Pp. 99 Analyze by flameless AA if
cone. <20 yg/l

ca p. lol Analyze by flameless AA if
on conc. <20 ug/l

cr Pp. 105 Use nitrous oxide-acetylene
flame for all analyses--analyze
by flameless AA if cone. <200 ug/l

cu Pp. 108 Analyze by flameless AA if
conc. <50 ug/l

Ni p. 141 Analyze by flameless AA if
conc. <100 pg/l

Pb p. 112 Analyze by flameless AA if
cone. <300 ug/l

an p- 155 Analyze by flameless AA if
. cone. <20 ug/l

*In those instances where more vigorous digestion for sample
preparation is desired (or necessary) the procedure on page 82
(4.1.3) should be followed.

b) Standard solutions to be used for the flameless
work should also be prepared as described in
"Methods for Chemical Analysis of Water and Wastes
(1974)" (Reference 7). The working standards should
be diluted to contain the same acid concentration as
the prepared samples. The instrumental settings
and conditions recommended by the manufacturers are
to be considered the procedural guidelines. In

addition, the following requirements should also be

incorporated into the procedures:


-17-
a vepresentative portion of the suspended solids that are
present. No specific method is required but a motor driven

mechanical stirrer with a propeller type blade is suggested.

Stirring with metal devices is acceptable for organic sampling.

Transfer the sample from the composite container through
a glass funnel into a 2-liter graduated cylinder and measure
the volume. Then transfer to a 4-liter separatory funnel or
a continuous extractor as described below. Rinse the cylinder
with several portions of the first volume of extracting sol-
vent. Note: [Either separatory funnel or continuous ex-
traction is acceptable for isolation of the organics. Contin-
uous extraction must be used when emulsions cannot be broken.

See discussion under Emulsions.]

Base-Neutral Extraction

Separatory Funnel Extraction -. Adjust the pH of the sample
with 6 N NaOH to ll or greater. Use multirange pH paper for
the measurement. Serially extract with 250 x 100 x 100 ml
portions of aistilled-in-glass methylene chloride. (About 40 mi
of the first 250 ml portion will dissolve in the sample and not
be recovered.) Shake each extract for at least 2 min by the

clock.

Dry and filter the solvent extract by passing it through
a short column of sodium sulfate. Concentrate the solvent by
Kuderna-Danish (K-D) evaporation (distillation). The sodium

sulfate should be prewashed in the column with methylene


fable IV. Base-neutral Extractables (Cont‘d.)
rat? Limit of
(hexachloro- Deteation Characteristia -

Compound Name benzene) (ng) BI ions (Rel. Int.)
chrysene 1.46 40 228(100), 229(19), 226(23)
bis (2~ethylhexy1) phthalate 1.50 40 149(100), 167(31), 279 (26)
benzo (a) anthracene 1.54 40 228100), 229(19), 226(19)
benzo (b) fluoranthene 1.66 40 252(100), 253(23), 125(15)
benzo (k) fluoranthene 1.66 , 40 252(100), 253(23), 125(16)
benzo (a) pyrene 1.73 40 252(100), 253(23), 125(21)
indeno (1, 2,3-cd) pyrene 2.07 100 276(100), 138(28), 277(27)
dibenzo (a,h) anthracene 2.12 100 278 (100), 139(24), 279(24)
benzo(qg h i)perylene 2.18 100 276 (100), 138(37), 277(25)
N-nitrosodimethylamine 42(100), 74(88), 44(21)
N-nitrosodi-n-propylamine 130(22), 42(64), 101(12)
4-chloro-phenyl phenyl ether 204(100), 206(34), 141(29)
endrin aldehyde :
3,3'-dichlorobenzidine 252(100), 254(66), 126(16)
2,3,7,8-tetrachlorodibenzo-

p-dioxin 322(100), 320(96), 59(95)
bis (chloromethyl) ether 45(100), 49(14), 51(5)
deuterated anthracene (d10) 1.09 40 188(100), 94(19), 90(18)

1

14 SP-2250 on 100/120 mesh Supe}coport in a6

Program: 50° for 4 min, then 8 /min to 260° and hold for 15 min,

* Conditioning of column with base is required.

cr ions

(Methane)

228, 229,
149
228,
252,
252,
252,
276,
278,
276,

229,
253,
253,
253,
277,
279,
277,

189, 217

‘x 2 mm id glass column; He @ 30 ml/min;

257

257
281
281
281
305
307
305


- 65 -

Field Blank Procedure for Automatic Samolers

Blank Water - Blank water must be as free from organic
interferences 2s possible. The analytical laboratory should
supply this water in bulk glass containers (minimum of five
liters) for field use. The supplying laboratory shall analyze
the blank water to determine the organic background that may be
present.

Procedure - All parts of the sampling system must be scrubbed
with hot detargent water and thorcughly rinsed with tap water and
blank water prior to use. Further rinsing with methylene
chloride is required when parts permit, i.e., are not suscestible
to dissolution by the solvent. (Hate: Tygon plastic tubing is a
source of phthalate ester cantaminaticn. Where its use is .
requiréd, j.e., in the peristaltic pump, the length must be kept
as short as possible. Teflon is acceptable and may be used in
other parts of the samaling system as in intake lines. In the
field, pump two liters of blank water through the sampling Tine
and pump tubing and discard, Then pump three liters of blank
water through the system and collect as a blank in a l-gallon
sample bottle that has been prepared as described below. Seal
the bottle with a Teflon iined cap. Immadiately fce the blank (4
C) and maintain at (4°C) during the transport and storage prior
to analysis. .

Composite Container - Prepare narfew-mcuth glass sample
bottles for use by washing with hot detergent water and
thoroughly. rinsing with tap water and blank water. Heat the
bottles at 400°C in a muffle-furnace or dry heat sterilizer for
30 minutas cr alternatively, rinse with methylene chloride and
air dry at recom temperature protected from atcmssheric or other
sources of contamination. Caps for tha bottles must be Tined
with Tefian which has bean solvent rinsed as above.

2. Collection of Grab Semoles

Collect grab samples ( minimum of one per day) for the
analysis of phenol, cyanide, and volatile organtcs
(purgable). Collect samples from the raw procass discharge,
the treated effluent, and the treated effluent after
chlorination, when chlorination is practicad. [t fs
recommended that the samples te callectad frem mid-channel
at mid-deoth. ‘Samples should be collected -et a turbulent,
well mixed saction of the channel.


PHENOLS .......-

Sample Preparation .

Procedure ....
Quality Assurance

Reporting of Data
REFERENCES ..-. 2» «

APPENDIX I .....-.
APPENDIX IIT ......
APPENDIX III .....

- 50

50
50
50
50

§1

53
55
63


- 69 -

site to determine whether or nct preservative is needed. If
Preservatation is required, collect teth preserved and non-
preserved samples. Wrap the samples with water proat packing
material, place in an insulatad chest and ice at 4°C. Maintain
at 4°C during transport and storage prior to analysis.

3. Identification of Samoles

ATl samples and blanks must be carefully identified
using water proof labels and water prec? ink. Include the
following information on the label: sempie number, date and
hour of sampling, comalete information as te source and
sampling point, oraservative added, if any, and name of
persen collacting the semale (include addrass and¢/er phone
number).


- 68 -

Organics (Purge and Trap Method)

Containers - Use 45 t0125 ml screw cap glass vials with
Teflon faced silcone septa: os

Vials (2)~ Pierce #13074 or equivalent
Septa(2)- Pierce #12722 or equivalent

Wash the bottles, septa, and caps with hot water and
thoroughly rinse with tap water and blank water. Heat the :
bottles and septa at 105°C for one hour, cocl to room temperature
in an enclosed contaminant free area. When cool, seal bottles
with septa (Teflon side down) and screw cap. Maintain the
bottles in this conditicn until just prior to filling with blank
water or sample.

(a) avattable from Pierce, Inc. Box 117, Rockford, IL 61105.

Collect dusticates 45-125 ml samples each time samoles are
collected. Two biank water samples, sealed in 45 ml vials, are
to accompany the sample bottles curing shipment to and from the
sampling site. If preservation for residual chlorine is to te
used, collect four samples during each sampiing peried. Two
should be preserved and twa not preserved. Two preserved and two
non-preserved blanks are to be provided.

Filling and Sealing cattlés - Slcwly fill each container to
overflowing. Carefully set the container on & level surface.
Place the septum (Teflon side down) on the convex sample
meniscus. Seal the sample with the screw cap. To insure that
the sample has Geen croperly sealed, invert the sample and
lightly tap the lid on a solid surface. The absence of entrapped
air bubbles indicatas a proper seal. If air bubbies are present,
open the bottle, add additional sample, and reseal. The sample
must remain hermetically sealed until it is analyzed.

Preservation - Preservative (sodium thiosulfate or sodium
bisulfite) is used to stabilize samples containing residual
chlorine. The production of chlcreform and other haloforms
continues in such samples if they are not stabilized. Waste
streams that have been treated with chlorine shauld be tasted on


- 28 -
factors, therefore, must be calculated to compare the MS
response for known quantities of each priority pollutant with

that of the internal standard. The response ratio (R) may

be calculated as:

Ac ca
R= ka * Ge

where Ac is the integrated area of the characteristic ion from
the specific ion plot for a known concentration, Cc. Aa and
Ca are the corresponding values for deuterated anthracene.

The relative response ratio for the priority pollutants

should be known for at least two concentration values--40 ng
to approximate 10-ppb and 400 ng to approximate the 100 ppb
level. Those compounds that do not respond at either of these
levels may be run at concentrations appropriate to their res-
ponse. For guidance in MS limits of detection refer to the

values given in Tables III-v.

The concentration of a compound in the extract may now
be calculated using:

c- Bae

where C is the concentration of a component, Ac is the inte-
grated area of the characteristic ion from the specific ion
plot, R is the response ratio for this component, Aa is the
integrated area of the characteristic ion in the specific

ion plot for deuterated anthracene, and Ca is the concentration

of deuterated anthracene in the injected extract.


-14-
Table II

Characteristic Ions of Volatile Organics

EI Ions (Relative Ion used to
Compound intensity) quantify
chloromethane $0(100); 52(33) 50
dichlorodifluoromethane 85(100); 87(33);

” 101(13); 103(9) 101
bromomethane 94(100); 96(94) 94
vinyl chloride 62(100); 64(33) : 62
chlorcethane 64(100); 66(33) 64
methylene chloride 49 (100) ;51(33);

84(86}; 86(55) 84
trichlorofluoromethane 101(100); 103(66) lol
1,1-dichloroethylene 61(100); 96(80); 98(53) 96
bromochloromethane (IS) 49 (100); 130(88); ,

128(70); 51(33) 128
1,1-dichloroethane 63(100); 65(33); 83(13);

85(8); $8(7); 100(4) 63
trans-1,2-dichloroethylene 61(100); 96(90); 98(57) 96
chloroform 83(100); 85(66) 83
1,2-dichloroethane 62(100); 64(33);

98(23); 100(15) 98
1,1,1l-trichloroethane 98(100); 99(66);

117(17); 119(16) 97
carbon tetrachloride 117(100); 119(96); 121(30) 117
bromodichloromethane ~ 83(100); 85(66); .

127(13); 129(17) 127
bis-chloromethyl ether 79(100); 81(33) 79
‘1,2-dichloropropane 63(100); 65(33);

112(4); 114(3) 112
trans-1,3-dichloropropene 75(100): 77(33) 75
trichloroethylene 95(100); 97(66);

130(90); 132(85) 130
éibromochloromethane 129 (100); 127(78);

. 208(13); 206(10) 127

cis-1,3-dichloropropene 75 (100); 77(33) 75


. - 20 -
separatory funnel and through the sample and
emulsion.

Other ideas include stirring with a glass rod, heating
on a steam bath, addition of concentrated sodium sulfate

solution, and sonication. See discussion in Appendix I.

“- Continuous Extraction - If you cannot achieve 85% solvent
recovery, start with a fresh aliquot of sample and extract by

continuous extraction.

Adjust the pH of the sample as appropriate, pour into
the extractor, and extract for 24 hours. When extracting a
2-liter sample, using the suggested equipment, two liters of

blank water must be added to provide proper solvent recycle.

For operation, place 200-300 ml of solvent in the ex-
tractor before the sample is added and charge the distilling
flask with 500 ml of solvent. At the end of the extraction
remove the solvent from the distilling flask only and evas-
orate and treat as described in the base-neutral extract

section.

Blank Extraction: It is not entirely certain that
2 liters of blank will always be available. When it is,
proceed to process it as the corresponding sample was done.
Include any emulsion breaking steps that used glass wool,
excess solvent or additional chemicals. If less than 2 liters
is available, measure the blank and bring it to volume with
distilled water. On analysis make the necessary quantita-

tive corrections.


- 16 -

Organics by Liquid-Liquid Extraction -

Gas Chromatography

Scope
. This method is designed to determine those "unambiguous
priority pollutants" associated with the Consent Decree, that
are solvent extractable and amenable to gas chromatography.
These compounds are listed in Tables III to V of this section.
Except for the pesticides, it is a gas chromatographic-mass
spectrometric method intended for qualitative and semi-
quantitative determination of these compounds during the ,
survey phase of the industrial effluent study. Pesticides
are initially determined by electron capture-gas chromatography

and, qualitatively, confirmed by mass spectrometry.

Special Apparatus and Materials

Separatory funnels - 2 and 4-liter with Teflon stoscock

Continuous liquid-liquid extractors - any such apparatus
designed for use with solvents heavier than water
and having a capacity of 2 to S5-liters (a) - Con-
necting joints and stopcocks must be of Teflon or

glass with no lubrication.
Procedure

Sample Preparation for GC-MS Survey - Blend the com-

posite sample to provide a homogeneous mixture including

(a) Available from Aldrich Chemical Co., Milwaukee, WI,
Catalog No. 210, 157-5.


- 29 -

In samples that contain an inordinate number of inter-
ferences the chemical ionization (CI) mass spectrum may make
identification easier. In Tables rv and v characteristic
CI ions for most compounds are given. The use of chemical

ionization MS to support EI is encouraged but not required.
Quality Assurance

GC-MS system performance evaluation is required each day
the system is used for samples or reagent blanks. A sample

of 20 ng of decafluorotriphenylphosphine (b)

is injected into
the system and the mass spectrum is acquired and plotted.
Criteria established in Reference 2 must, be met. The analyst
must also demonstrate that the analytical conditions employed
result in sharp total ion current peaks for 40 ng of benzidine
on the SP2250 column when this column is used and 100 ng of
pentachlorophenol on the Tenax GC column when it is used with

the MS as a detector. All plots from the performance evalu-

ation must be retained as proof of valid performance.

As performance evaluation samples become available fron
EMSL-Cincinnati, they are to be analyzed by solvent extraction
once each 20 working days and the results reported with other

analytical data.

The 1% SP2250 and Tenax GC column packings are available

by request to EPA contractors from Dr. Walter Shackelford, EPA,

Athens, GA.

(b) Available from PCR, Gainesville, FL


-il1l-

Quantify samples by comparing the area of a single. mass
(see Table II) of the unknown in a sample to that of a stan-
dard. When positive responses are observed, prepare and
analyze a reference standard so that the standard response
closely approximates the sample response. Calculate the con-
centration in the sample as follows:

{Area for unknown)

(Axvea_ for Standard) -
Concentration of standard (ug/1) 7 "9/1 of unknown

Reporting of Data
Report all results to two significant figures or to the

nearest 10 ug/l. Report internal standard data to two signif-

icant figures.

As the analyses are completed, transfer GC-MS data to
magnetic tape as described under reporting of data in method
for "Organics by Liquid-Liquid Extraction ~ Gas’ Chromatography."

Report all quality control (QC) data along with the
analytical results for the samples. In addition, forward

all QC data to EMSL, Cincinnati.

Direct Aqueous Injection Gas Chromatography

As noted in the Scope, Acrolein and acrylonitrile should
be analyzed by direct aqueous injection gas chromatography-
mass spectrometry. See references (3), (4), and (5) for

these methods. The detection level for these methods is 0.1

mg/l and above.


- 55 -

Appendix II

Possible Sources for Some Priority Pollutant Standards

. Source of
Compound. Standard?
acenaphthene AN p. 118
acrolein AL p. 18
acrylonitrile AL p. 19
aldrin HERL #30
dieldrin HERL 22380
benzene Bp. 154
benzidine! RFR
carbon tetrachloride (tetrachloromethane) Bp. 88
chlordane (technical mixture & metabolites) HERL #1200
Chlorinated benzenes (other than dichlorobenzenes)
chlorobenzene AL p. 165
1,2,4-trichlorobenzeneTM AL p. 710
hexachlorobenzene AL p. 416
Chlorinated ethanes (including 1,2-

dichloroethane, 1,l1,1-trichloroethane

and hexachloroethane)
1,2-dichlorcethane AL p. 261
1,1,1-trichloroethane Bp. 309
hexachloroethane AL p. 416
1,l-dichloroethane . PB p. 142
1,1,2-trichlorcethane PBs. 389
1,1,2,2-tetrachloroethane PB p. 372
chloroethane EA >. 53
Chloroalkyl ethers (chloromethyl, chloroethyl and

xed ethers
bis (chloromethyl) ether? RFR
bis (2-chloroethyl) ether AL p. 173
2-chloroethyl vinyl ether AL p. 174

Chlorinated naphthalene

2-chloronaphthalene ICM p. 50


" Procedure

Preparation of Standards - Prepare standard stock solu-
tions (approximately 2 ug/ul) by adding, from a 100 ul syringe,
1 to 2 drops of the 99+% pure reference standard to methanol
(9.8 ml) contained in a tared 10 ml volumetric flask (weighed
to nearest 0.1 mg). Add the compound so that the two drops
fall into the alcohol and do not contact the neck of the flask.
Use the weight gain to calculate the concentration of the stanc-
ard. Prepare gaseous standards, i.e., vinyl chloride, in a
similar manner using a 5 ml valved gas-tight syringe with a
2 in. needle. Fill the syringe (5.0 ml) with the gaseous. com-
pound. Weigh the 10 ml volumetric flask containing 9.8. ml of
methyl alcohol to 0.1 mg. Lower the syringe needle to about
5 mm above the methyl alcohol meniscus. Slowly inject the
standard into the flask. The gas rapidly dissolves in the
methyl alcohol. Reweigh the flask, dilute to volume, mix,
tightly stopper, and store in a freezer. Such standards are
generally stable for at least one week when maintained at less
than 0°c. teck standards of compounds which boil above room
temperature are generally stable for at least four weeks when

stored at 49C.

{Safety Caution: Because of the toxicity of most organo-
halides, primary dilutions must be prepared in a hood. Fur-
ther, it is advisable to use an approved respirator when

handling high concentration of such materials.]


~26-

should also be equipped with mass storage devices for
saving all data from GC-MS runs. There should be computer
software available to allow searching any GC-MS run for
specific ions and plotting the intensity of the ions with
respect to time or scan number. The ability to integrate

the.area under any specific ion plot peak is essential for

quantification.

To indicate the presence of a compound by GC-MS, three
conditions must be met. First, the characteristic ions for
the compound (Tables III-v) must be found to maximize in the
same spectrum. Sécond, the time at which the peak occurs
must be within a window of + 1 minute for the retention time
of this compound. Finally, the ratios of the three peak
heights must agree with the relative intensities given in

Tables III-v within + 20%.
An example of identifying a component is as follows:

It is knewn that hexachlorobenzene elutes from the SP2250
column at 19.4 minutes. Hexachlorobenzene has characteristic
mass ions at 284(100%), 142(30%), and 249(24%). The computer
is asked to display a plot of the intensities of these ions
versus time (or MS scan number) and the window from 19.4-20.4
minutes is examined for the simultaneous peaking of the in-
tensities of these ions. If all three ions are prasent, the
ratio of the peak heights is checked to verify that it is
100:30:24 + 20%. If the three tests are successful, hexachloro-

benzene has been identified in the sample.


- 62 -
REQUEST FOR ANALYTICAL REFERENCE STANDARDS

Date

Date Request Recd i /
70: Quality Assurance Section Shipment Date 7
Enviromental Toxicolegy Division, Lab Code No.

EPA, HERL, Research Triangle Park, NC 27711 | Order Filled by
MD-69 CO NOT WRITS IN THIS SSACz

The following reference standazds azé required for our program:

Catalog Compound Catalog Compound
Code (Catalog Name) Code (Catalog Name)
Ro.

No.

: |

| ee | el ae J}

If necessary, use back of sheet to complete list. Covering letter unnecessary
if this form is completed in full.

Name and address of laboratory,

Requestozr's Name (Frint or tyve)
IMPORTANT: a ;
tL. The amount of each standard is restricted to 100 ag because of the scarcity
and exgense of refining analytical grade saterials.

2. Please retumn at once. the acknowleégement card enclosed with each shisnent.
This provides the sole evidance of éslivery of the shisment.

3. De not request ccomzounds not listed in the catalog. Mo gthers ara stocked.

4. If a bottle appears to be empty, Tesove CaP and examine interioz> of botzle
_and ¢ap. Certain highly viscous saterials tend to collect in cap.


- 64 -

as outlined below. New unused tubing must be used for the
sampling line and for the pump for each individual outfall or
sample location. Vacuum type autcmatic samplers may be used
provided that the sample chambers are glass and that they are
cleaned after every use as outlined for glass comoasite
Containers. Place the sampler or composite container in an
insulated chest and ice. Maintain the sample at 4°C during
the compositing pracedure. At the completion cf the
compositing period seal the container with a teflon lined
cap. Place the container in an insulatad shipping container,
tea, and seal, then ship to the analytical laboratory.

Maintain at 4°C during transport and storage prior to
analysis. : .

When sampling raw untreated industrial discharges which
are generally high in suspended solids it fs imperative that
adequate sample flow rata te maintained throughcut the sample
train fn order te effectively transsort the solids. In.
horizantal runs, the velocity must excaed the scour velocity,
while in vertical runs the sattling or the fali velocity must
be exceeded several times to assure adequate transcort of
solids in the flow. The equipment used in samgTing raw
discharges then must have a minimum intake velocity of 2 feet
per second. In the sampling of treated effluents just about
any commerically available automatic liquid samaler cculd be
used.

When more than ane laboratory is invoived in the
analysts of the various parameters, the sample should i7 at
all possible not be divided in the field but rather at the
contractors’ laboratory. Fer purpose cf this pregram the
compesite will be divided into four parts, ane part for
metals. analysis, one for pesticides and PC3's, one fer GC/MS
compounds and one for the classic peramatars.

Blend the composite sample to provide a homegenecus
mixture including a representative suspension ef any solids
jn the container. No specific method is required, hand
stirring with clean glass or taflon reds, mechanical paddles
or magnetic mixing with teflon coated stirring tars may be
used. Metal mixing devicas may not be used.

Metals - Withdraw a well blended aliquot of the
composita sample. Using a glass funnel, rinse the sample
container with a small portion of the sample, then transfer


- 65 -

250 - 500 ml of sample to the bottle. Oo not add any
reservative to the sample just seal and prepare for
shipment. AIT samples must be carefully identified using
Jabeles supplied by EGD. Indicate on the label whether the
sample is a raw discharge or treated effluent as shown. If

sample is to be run on the plasma unit only indicate so at

base of tag. Ship samples to the Chicago Regional Laboratory
at the addressed shown.

U.S. Environmental Protection Agency
Region V, Central Regional Laboratery
1819 W. Pershing Road

Chicago, Illinois €0609

Raw discharge or treated effluent
eff ~ Na vo02200

ton

Lacs

Sameier.

Samote Point

Gra,

Tyae Samate, Composite
Tyo" See

Ti a
Prenrativei gape

Plasma only


- 23 -

Specific source or stage of traatment
Date sampled

Date sealed

Name of contractor and analytical Laboratory

Wrap the ampuls in packing material to prevent breakage
and’ mail or ship them postpaid at ambient temperature. When
the samples are safely in ampuls, the remainder of the conm-

posite sample may be discarded.

GC-MS Analysis

Compounds to be analyzed by GC-MS alone fall into two
categories--those in the base-neutral extract (Table Iv) and
those in the acid extract (Table v). Pesticides (Table III
that were tentatively identified in the pesticide analysis

will be confirmed by GC-MS.

The base-neutral extractables may be separated and eluted

into the MS unéer the following chromatographic conditions:

Colum - 6 fcot, 2.0 mm inside diameter, glass

Packing - 18 $P2250 on 100/120 mesh Supelcorort.

Program - hold 4 minutes @ 30°, program 50°-2500
@ 8°/min., hold 20 minutes ¢260°

Injector - 275°

Separator - 275°

Carrier gas - Ze @ 30 ml/min

Injection size - >2 ul


Table
Table
Table
Table
Table
Table

Table
Table

LIST OF TABLES

I. Elution Order of Volatile Priority Pollutants
II. Characteristic Ions of Volatile Organics . .
III. Pesticides . 2. 2. 1 6 2 0 ee we ee ewe
IV.. Base-Neutral Extractables .....-. 2. 2 « es
V. Acid Extractables . 2... ee ee eee eee
VI. Elution Order of Most of the Semivolatile
Priority Pollutants .. 2... es. e ee ee
VII. Order of Elution for OV-17 SCOT Column . .

VIII. Metals 2... 2 2 ee eee ee ee ee

12
14
33
34
36

37
41
45


Appendices

I. General Information
Ir. Possible Sources for Some Priority Pollutant Standards

tIr. Collection of Samples for Screening Analyses


Compound

chloromethane
dichlorodifluoromethane
bromomethane

vinyl chloride
chloroethane

methylene chloride
trichlorofluoromethane
1,1l-dichloroethylene
bromochloromethane (IS)
1,1-dichloroethane
trans-1,2-dichloroethylene
chloroform
2,2-dichloroethane
1,1,1-trichloroethane
earbon tetrachloride
bromodichloromethane
bis-chloromethyl ether
1,2-dichloropropane

(da)

trans-1,3-dichloropropene
txichleroethylene
dibromochloromethane
cis-1,3-dichloropropene
1,1,2-trichloroethane
benzene

2-chlorcethylvinyl ether
2-bromo-1-chloropropane (IS)
bromoform
1,1,2,2-tetzachloroethene

-12-

Table I
Elution Order of Volatile Priority Pollutants ‘@)
Purging
Efficiency
Purging Modified
(b) Efficiency Method

RRT (percent) (percent)

0.152 91

0.172 a 100 ‘¢)

0.181 85

0.186 lol

0.204 90

0.292 76

0.372 96

0.380 97

0.457 88

0.469 89

0.493 92

0.557 95

0.600" 98

0.672 94

0.684 87

0.750 92

0.760 0

0.818 92

0.847 90

0.867 89

0.931 87

0.913 85

0.913 88

0.937 no data

0.992 no data

1.000 92

1.115 71

1.262 88

1.281 38

1,1,2,2-tetrachloroethane


2.

-2-
for the purge and trap method are, generally, not suitable for

the determination of compounds eluting later than chlorobenzene.

Special Apparatus and Materials

Sample extraction apparatus (minimum requirements) :

S-ml glass syringes with Luer-Lok - 3 each

2-way syringe valves (Teflon or Kel-F) - 3 each

8-inch, 20 gauge syringe needle - 2 each

S-ml glass, gas-tight syringe, pressure-lok (a)
or equivalent - 1 each

Tekmar Liquid Sample Concentrator, model LSC-1 (b)
or equivalent. Includes a sorbent trap
consisting of 1/8 in. O.D. (0.09 to 0.105
in. I.D.) x 6 in. long stainless steel tube
packed with 4 inches of Tenax-GC (60/80 mesh
and 2 inches of Davison Type-15 silica gel

(35/60 mesh).

Gas Chromatographic Column Materials

Stainless steel tubing 1/8 in. O0.D. (0.09 to 0.105 in.
I.D.) by 8 ft. long. Carbopack C (60/80 mesh) coated with

0.2% Carbowax 1so¢ ©) + Chromosorb-W (60-80 mesh) coated with
3% Carbowax 1500. :

(a) Available from Precision Sampling Corp., P.O. Box 15119,
Baton Rouge, LA 70815.

(b) Available from Tekmar Company, 2.0. Box 37202,
Cincinnati, OH 45222.

(c) Available from Supelco, Supelco Park, Bellefonte, PA
16823. Stock No. 1-1826.


-18 -

chloride. (Note: Check sodium sulfate blank and, if
necessary, heat in an ‘oven at 500°C for 2 hours to remove
interfering organics.] After drying the extract, rinse the

sodium sulfate with solvent and add to the extract.

Evaporate the extract to 5-10 ml in a 500 ml K-D apparatus
fitted with a 3-ball macro-Snyder column and a 10 ml calibrated
receiver tube. Allow the K-D to cool to room temperature.
Remove the receiver, add fresh boiling chips, attach a two-
chamber micro-Snyder column and carefully evaporate to 1.0 ml
or when active distillation ceases. Remove the micro-Snyder
column and carefully evaporate to 1.0 ml or when active dis-
tillation ceases. Remove the micro-Snyder column and add the
internal standard: 10 pl of 2 ug/ul d, g~anthracene (per each

ml of extract). Mix thoroughly.

Tf it is to be overnight or longer before the extract is
run by GC-MS, transfer it from the K-D ampul with a disposable
pipet to a solvent tight container. The recommended container
is a standard 2 ml serum vial with a crimp cap lined with
Teflon coated rubber. These are inert and methylene chloride
can be held without evaporation loss for months if caps are
unpierced. When the extracts are not being used for analysis,
store them with unpierced caps in the dark and at refrigerator

or freezer temperatures.

Acid (Phenols) Extraction - Adjust the pH of the base-

neutral extracted water with 6 N 2Cl to 2 or less. Serially


SAMPLING AND ANALYSIS PROCEDURES FOR

SCREENING OF INDUSTRIAL EFFLUENTS FOR PRIORITY POLLUTANTS

U. S. ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
. CINCINNATI, OBIO 45268

MARCH, 1977
Revised

APRIL, 1977


- 41 -

Table VII. Order of Elution for
OV=-17 SCOT Column

Compound

1,3-dichlorobenzene
1,4-dichlorobenzene
2-chlorophenol
1,2-dichlorobenzene
bis (2-chloroethyl) ether
phenol

bis (2+chloroisopropy1) ether
hexachloroethane
nitrobenzene
2-nitrophenol
1,2,4~-trichlorobenzene
2,4-dimethylphenol
naphthalene
2,4-dichlorophenol
hexachlorobutadiene
isophorone
p-chlore-m-cresol
hexachlorocyclopentadiene
2,4,6-trichlorophenol
chloronaphthalene
2,4-dinitrotoluene
acenaphthylene
acenaphthene
dimethylphthalate
fluorene
diethylphthalate
H-nitrosodipnenylamine
2,6-dinitrotoluene
@-BaC

4-bromophenyl phenyl ether
¥~-BEC
hexachlorobenzene
8-BHC

phenanthrene
anthracene
di-n-butylphthalate
aldrin

fluoranthene

pyrene

DDE

DDD

endrin

dieldrin

DDT .

butyl benzyl phthalate
benzo (a) anthracene

chrysene

Spectrum Number?

134
137
141
153
163
165
173
178
194
219
234
240
240
244
262
272
317
325
332
339
372
374
390
397
434
447
447
454
476
478
487
490
506
518
518
583
592
617
634
659
664
688
688
713
713
748
748


. a 5 >
pour the sample into one of the syringes until it overflows.
Replace the syringe plunger and compress the sample. Open
the syringe valve and vent any residual air while carefully
adjusting the volume to 5.0 ml. Then close the valve. Fill
the second syringe in an identical manner from the same
sample bottle. Use the second syringe for a duplicate analy-
sis as needed. Open the syringe valve and introduce 5.0 ul of
the internal standard mixture through the valve bore, then
close the valve. Attach the 8-inch needle to the syringe
valve and inject the sample into the purging device. Seal
the purging device and purge the sample for 12 minutes. The
purged organics are sorbed on the Tenax-silica gel trap at

room temperature (20-259C).

While the sample is being purged, cool the gas chromato-
graphic column oven to near room temperature (20-309C). To -

ao this, turn heater off and open column oven door.

At the completion of the 12-minute purge time, inject
the sample into the gas chromatograph by turning the valve
to the desorb position. Hold in this position for four min-
utes while rapidly heating the trap oven to 180°C, then return
the valve to the purge position, close the GC column oven
door, and rapidly heat the GC oven to 60°C. Consider this
time zero and begin to collect retention data. Hold at 60°C
for four minutes, then program at 8°/minute to 170°C and hold

, until all compounds have eluted. Begin collecting GC-MS


-4-

From the primary dilution prepare a secondary dilution
mixture in methyl alcohol so that 20.0 ul of the standard,
diluted to 100.0 ml in organic free water, will give a stand-
ard which produces a response close to that of the unknown.
Also prepare a complex test mixture at a concentration of
100.ng/yl containing each of the compounds to be determined.
Prepare a 20 ug/l quality check sample from the 100 ng/pl

standard by dosing 20.0 ul into 100.0 ml of organic free water.

Internal Standard Dosing Solution - From stock standard
solutions prepared as above, add a volume to give 1000 ug each
of bromochloromethane, 2~bromo-l-chloropropane, and 1,4-
dichlorobutane to 45 ml of organic free (plank water) con-
tained in a 50 ml volumetric flask, mix and dilute to volume.
Prepare a fresh internal standard on a weekly basis. Dose
the internal standard mixture into every sample and reference

standard analyzed.

Preliminary Treatment of Sample - Remove samples from
cold storage (approximately an hour prior to analysis) and
bring to room temperature by placing in a warm water bath

at 20-259C.

Purging and Trapping Procedure - Adjust the helium purge
gas flow to 40 ml/min. Set the Tekmar 2-way valve to the
purge position and open the purging device inlet. Remove
the plungers from two 5-ml syringes and attach a closed 2-way

syringe valve to each. Open the sample bottle and carefully


- §4-
APPENDIX I

(continued)

There is a justifiable concern that the extraction efficiency
for these compounds may differ widely depending on the nature of
the effluents. This is true but no better approach is apparent.
For example, recoveries of most of the base-neutrals were judged
to be about 75% from the tannery and petroleum samples but less

than 25% from soap and detergent.

Acid (Phenol) Analysis

Although the 1l phenols of interest here do chromatograph on
the Tenax colum cited, the chromatography is poor, particularly
for the nitrophenols. Two other columns have shown good response
for the acid extractables. $P2250 can be used for this purpose.
Phenol responses on SP2250 are shown in Table Iv. It should be
noted, however, that 4-nitrophenol, 2,4-dinitrophenol, 4,6-dinitro-
o-cresol, and pentachlorophenol failed to give MS response at the

100 ng level using this column.

.SP1000 (4% load) has also been evaluated for use with the
acid fraction. All but 2,4-dinitrophenol and 4,6-dinitro~-o-cresol
elute from this column. Pentachlorophenol and 4-nitrophenol are
eluted from SP1000, but they produce broad peaks which are difficult

to quantify-


-37-

Table VI. ELUTION ORDER OF MOST OF THE SEMIVOLATILE
PRIORITY POLLUTANTS ON 1% $Pp2250°

Compound rere
1,3-dichlorcbenzene 0. 35%
2-chlorophenol 0.35°
1,4-dichlorobenzene 0. 36%
hexachloroethane 0.38
1,2-dichlorobenzene . 0.39
bis (2-chloroisopropyl) ether 0.47
8-endosulfan 0.51
2,4-dimathyl phenol 0.52°
2-nitrophenol 0.53°
2,4-dichlozophenol 0.53°
hexachlorobutediene 0.55
1,2,4-trichlorobenzene 0.55
naphthalene 0.57
bis (2-chloroethyl) ether 0.61
hexachLlorocyclopentadiene 0.64
nitrobenzene 0.64
phenol 0.67
bis (2-chloroethoxy) methane 0.68
2,4,6-txichLorophenol o.71°
p-chloro-m-cresol 0. 73°
2-chloronaphthalene 0.76
aceanaphthylene 0.83
acenaphthene 0.86
isophorone 0.87

fluorene Q.91


- 25 -
and in addition, the system must be shown to elute the late

running polynuclear aromatic compounds.
The acid extractables may be chromatographed as follows:

Column, 6 foot, 2.0 mm inside diameter, glass
Packing ~ Tenax GC, 60/80 mesh

Program - 1809 - 3009 @ 8°/min

Injector - 290°

Separator - 290°

Carrier Gas - He @ 30 ml/min

Injection size - >2 ul

Table Vv lists the 11 acid extractables in order of:
relative retention times (compared to 2-nitrophenol). Chroma-
tography of nitrophenols is poor. The limits of detection
given refer to the amounts required to get MS confirmation

by the methods described below. See Appendix I.

Before an acid extract is run on the GC-MS the operator
should demonstrate the ability to detect 100 ng of penta-
chlorophenol. :

Mass Spectrometry should be conducted with a system
utilizing a jet separator for the GC effluent since membrane
separators lose sensitivity for light molecules and glass
frit separators inhibit the elution of polynuclear aromatics.
A computer system should be interfaced to the mass spectro-
meter to allow acquisition of continuous mass scans for the

auration of the chromatcgraphic program. The computer system


- 42 -
_Table VIZ. Continued

Compound Spectrum Number?
bis (2-ethylhexyl) phthalate 804
benzo(a)pyrene 906
benzo (b) fluoranthene . 970
benzo (k) fluoranthene 970

1 33 meter glags ov-17 scoz column,
Program: 60° =~ 260° @ 6 /minute

2 Number of 2.5 second scans up to point of elution.


-24-

Table Iv lists the 49 base-neutral extractable compounds
in order of relative retention times (compared to hexachloro-
benzene) for the above GC conditions. Detection limits were
determined by MS response. The seven compounds without re-
tention times or limits of detection were not available for
this. report. It is not recommended that 2,3,7,8-tetrachloro-
dibenzo-p-dioxin (TCDD) be acquired due to its extreme tox-
icity. Based on their similarity to compounds that were avail-
able all seven are expected to be chromatographable using
these standard conditions. In addition the characteristic

masses recommended for MS identification are listed in Table Iv.

The limits of detection given in Tables III and IV refer
to the quantity necessary to inject to get confirmation by

the MS methods described below.

At the beginning of éach GC-MS run of a base-neutral
extract, the cperator should demonstrate the ability to chro-
matograph benzidine at the 40 ng level. Only after this is
accomplished should the run be started. If benzidine can be
chromatographed, the other nitrogen-containing compounds of

fable IV can be chromatographed as well.

If desired, capillary or SCOT columns may be used instead
of the packed column of SP-2250. Coatings of OV-17 or S?-2250
may be used. The elution order of OV-17 and SP-2250 are very
similar. Some specific data for OV-17 is given in Table VII.

The performance criteria for benzidine must still be met


-61-

ENVIRONMENTAL TOXICOLOGY DIVISION
WEALTH EFFECTS RESEARCH LASORATORY
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Reseazch Triangle Park, North Carolina °27711

SUBJECT: Index of Pesticides Analytical Reference Jen 76
4 Standards ~ Update of Mailing List DATE: June, 19

FROM: Health ESfects Research Laboratory, ETD, AC3, a) Th <S
Research Triangle Park, NC, U.S.A. 27711 (uD-68) -~"7

To: All Laboratory Facilities on cur Mailing List

This copy of the 1976 revision of our pesticides reference standards

index was mailed to the address appearing qn our mailing list. As this

list is several years old, we are sure that a number of addresses have

changed and that some are probably no longer existent.

If you wish to remain on our. mailing list to receive future updates

of this publication, would you be good enough to complete the mail-back
below, snip it off, and return it to us. Do not tear off the back cover
to retum to the address shown. ‘ If you have no use for this publication
but know of some other individual within your organization whe is con-
cemsned with pesticides analysis, would you convey this index, along, with
the mailback, to that person.

fc: U. S. Environmental Protection Agency .
Health Effects Research Laboratory Date
Environmental Toxicology Division . ot
Research Triangle Park, NC, U.S.A. 27711 (0-69)

We wish to be retained on your mailing list to receive future updates
of the Pesticides Standards Index. The address shown on the envelose
is entirely correct and requires no changes.

We have no interest in future updates of this publication. Please
cancel us from your mailing list.

We wish to be retained on your mailing list, but the adéress shown
on the envelope should be changed to =ead (print or type)

Recipien


Organics by Purge and Trap -

Gas Chromatography

Scope
This method is designed to determine those “unambiguous

priority pollutants,” associated with the Consent Decree, that
are amenable to the purge and trap methoa ‘) . These compounds
are listed in Table I of this section. It is a gas chromato-
graphic-mass spectrometric (GC-MS) method intended for quali-
tative and semi-quantitative determination of these compounds

during the survey phase of the industrial effluent study..

Certain compounds, acrolein and acrylonitrile, are not

.efficiently recovered by this method and should be determined

by direct aqueous injection GC-MS. Direct aqueous injection

GC-MS is recommended for all compounds that exceed 1000 ug/l.

The purge and ‘trap and the liquid-liquid extraction methods
are complementary to one another. There is an area of overlap
between the two and some compounds may be recovered by either
method. However, the efficiency of recovery depends on the
vapor pressure and water solubility of the compounds involved.
Generally, the area of overlap may be identified by compounds
boiling between 130°C and 150°C with a water solubility of
approximately two percent. When compounds are efficiently re-
covered by both methods, the chromatography determined the 2

method of choice. The gas chromatographic conditions selected


- 15 -

Table (cont'd)

EI Ions (Relative Ion used to
Compound intensity) quantify
1,1,2-trichlorcethane 83(95); 85(60); 97(100);

99(63); 132(9); 134(8) 97
benzene 78 (100) . 78
2-chloroethylvinyl ether 63(95); 65(32); 106(18) 106
2-bromo-1-chloropropane(IS) 77(100); 79(33) 7156(5) 7
bromoform 171 (50) ;173(100); 175 (50);

250(4); 252(11); 254(11);

256 (4) 173
1,1,2,2-tetrachloroethene 129(64); 131(62);

164(78); 166(100) 164
1,1,2,2-tetrachloroethane 83(100); 85(66); 131(7);

133(7); 166(5); 168(6) 168
1,4-dichlorobutane (IS) §5(100)7 90(30); 92(10) 55
toluene 91(100); 92(78) 92
chlorobenzene 112(100); 114 (33) . 112
ethylbenzene 91(100); 106(33) 106.
acrolein 26 (49) 7 *27(100);

§5(84); 56 (83) 56
acrylonitrile 26(100); 51(32);

52(75)7 53(99) 53


- 52 -
9. “Handbook for Analytical Quality Control in Water and Waste-

w
water Laboratories (1972), U.S. Environmental Protection

Agency, Technology Transfer.
10. "Standard Methods for the Examination of Water and Waste-
water," 14th edition, 1975.


- 59 -
Appendix Ir

Possible Sources for Some Priority Pollutant Standards

(Continued)

. Source of
Compound Standard?
acenaphthylene AN p. 1
anthracene AN p. 118
1,12-benzoperylene AN p. 118
fluorene AN p. 118
phenanthrene AN p. 118
1,2:5 ,6-dibenzanthracene AN p. 118
indeno (1,2,3-C,D) pyrene AN p. 118
pyrene AN p. 118
2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) NI p. 174
tetrachloroethylene AL p. 680
toluene AL p. 701
toxaphene HERL #6740
trichloroethylene AL p. 711
vinyl chloride (chloroethylene) PB p. 406

l-promodecane (possible internal standard)
l-bromododecane (possible internal standard)

Footnotes.:

1

These compounds or any mixture containing 1% or more by weight
of these compounds are defined as carcinogens in the Federal
Register, Vol. 38, No. 144, pp. 20074-20076, 27 July 1973.
Prescribed safety regulations for handling are in the Federal
Register, Vol. 39, No. 20, pp. 3756-3797, 29 January 1974.

Only one source is listed even though several may be available
These sources are not to be interpreted as being endorsed by
the EPA; they serve to show at least one vender where each
standard can be obtained. When several sources were available
and compound purity was listed, the source having the highest
purity material was selected.

These compounds have been ordered but have not been received
at Athens. ERL as yet.



- 32 -
Other data formats are possible, but any format that is

used must be accompanied by a full explanation of all record

formats.

All magnetic tapes, documentation and a table of MS res-
ponse ratios should be sent to:

Dr. W. M. Shackelford

Athens Environmental Research Laboratory
College Station Road

Athens, GA 30601


Compound Name

fB-endosulfan
a-BHC

y-BHC

B-BHC

aldrin

heptachlor
heptachlor epoxide
a~-endosulfan
dieldrin

4,4'-DDE

4,4'-DDD

4,4*-ppt

endrin

endosulfan sulfate

6-BIIC
chlordane
toxaphene
PCB-1242
PcB-1254

“3 -

377 (10) **

fable IIl. Pesticides
newt Detection Limit Characteristic
(hexachlorobenzene) (ng) EI ions (Rel. Int.)
0.51 40 201 (100), 283(48), 278(30)
1.02 40 183(100), 109(86), 181(92)
1.09 40 -183(100),°109(86), 181(91)
1.12 40 181(100), 183(93), 109 (62)
1.14 40 66(100), 220(11), 263(73)
1.15 40 100(100), 272(60), 274(46)
1.23 Au 355(100), 353(79), 351(60)
1,24 40 201(100), 283(48), 278(30)
1.20 40 79(100), 263(28), 279(22)
1.30 40 246(100), 248(64), 176(65)
1.33 40 235(100), 237(76), 165(93)
1.38 40 235(100), 237(72), 165(59)
1.41 40 81(100), 82(61), 263(70)
1.41 20 272(100), 387(75), 422(25)
183(100), 109(86), 181(90)
1.14-1.37 373(19), 375(17),
1.22-1,47 (231, 233, 235)*
0,93-1.24 (224, 260, 294)*
1.18-1.41 (294, 330, 362)*

* hese ions are listed without relative intensities since the mixtures they represent
defy characterization by three masses.

** hese three ions are characteristic for the a and y forms of chlordane. No stock
should be set in these three for other isomers,

Program: 50 f

13 SP-2250 oR 100/120 mesh Supe},

coport in a,6' x 2 mm id glass column; He @ 30 m1/min;
or 4 min, then 8 /min to 260° and hold for 15 min.


- 48 -

c) For mercury, the spike added should be an
amount equal to five times the detection level.

d) Reagent blanks shall be run for each metal
being determined with the sample values being
corrected accordingly.

e) When using the method of standard addition, a
linear curve over the entire range of addition

is necessary for the results to be considered

valid.

5. Data Reporting

Report all metal concentrations as follows: Less than

10 ug/l, nearest ug; 10 ug/l and above, two significant figures.


-21-
Pesticides: These, compounds are to be analyzed by
EC-GC using the EPA methed published in the Federal Register,

Vol. 38, Number 125, Part II, pp. 17318-17323. (Friday,
dune 29, 1973). One-liter rather than 100 ml is to be ex-
tracted. The solvent amounts given in the method and other
parameters rémain unchanged. If pesticides are found by EC,
the extract is to be carefully evaporated (clean airstream)

to 0.5 ml and sent for GC-MS confirmation.

The compounds to be analyzed by EC-GC are listed in
Table IIr.

If the pesticide sample has-been received in a l-gal.
bottle, hand shake the bottle for 1 min. by the clock to evenly
suspend sediment. Pour the sample into a l-liter graduated
-cylinder and measure the volume. Then transfer the sample
to a 2-liter separatory funnel and rinse “the cylindes with
the first volume of extracting solvent. Use additional small
volumes cf solvent if necessary to transfer all of the sample.

Proceed with the extraction using the solvents and amounts

prescribed in the published method.

If the sample is to be taken izem the original composite
bottle, homegenecusly mix as ¢escribed earlier and transfer
a l-liter aliquot to a graduated cylinder, then transfer
to the separatcry funnel with the aid of a glass funnel and

rinse the cylinder as above.


1.

2.

7.

- 51 -

REFERENCES

“Determining Volatile Organics at Microgram-per-Liter Levels

by Gas Chromatography, T. A. Bellar and J. J. Lichtenberg,
Jour. AWWA, 68 ,739-744, Dec. 1974.

"Reference Compound to Calibrate Ion Abundance Measurements

in Gas Chromatography--Mass Spectrometry systems, J. W.
Eichelberger, L. E. Harzis and W. L. Budde, Anal. Chem. 47,
995-1900 (1975).

ASTM Annual Standards - Water, part 31, Method D2908 "Standard
Recommended Practice for Measuring Water by Aqueous-Injection
Gas Chromatography.” :
ASTM Annual Standards - Water, part 31, Method D3371 "Tentative
Method of Test for Nitriles in Aqueous Solution by Gas Liquid
Chromatograph.”

"Direct Analysis of Water Samples for Organic Pollutants

with Gas Chromatography-Mass Spectrometry," Harris. L. E.,

Budde, W. L., and Eichelberger, J. W. Anal. Chem., 46,
1912 (1974).

Federal Register, Volume 38, number 125, part II, Appendix II,
Pp. 17319, Friday, June 29, 1975, "Determination cf Organo-.
chlorine Pesticides in Industrial Eifluents,"

"Methods for Chemical Analysis of Water and Wastes (1974)

U.S. Environmantal Protection Agency, Technolegy Transfer.
"Determining Selenium in Water, Wastewater, Sediment and Sludé¢e
by Flameless Atomic Absorption Spectroscopy, T. D. Martin and

gc. F. Kepp, atomic Absorstion Newsletter, 14, 109-116 (1975).



w BE

cs

EA
ICN

PB

RFR

co
ter

- 60 -
Sources of Standards and Abbreviations
Aldrich Chemical Co., Milwaukee, Wisc.; Catalog 1977-1978.

Analabs, Inc., North Haven, Conn.; Catalog 18 (June 1976).
a. T. Baker Chemical Co., Phillipsburgh, N.d.;

Catalog 750 (July 1975).

“Chem-Service, West Chester, Pa.; Bulletin CS-100-8 (1975).

Chemical Procurement Laboratories, College Point, N.Y.;
1975 catalog. .

Eastman Kodak Co., Rochester, N.Y.; Catalog 43 (1976).

Rex Rare & Fine Chemicals, Plainview, N.¥.; Catalog No. 10
1975).

Nanogens International, P.O. Box 487, Freedom, CA 95019
"Nanogen Index" (1975). .

Pialtz & Bauer Chemical Co., STamford, Conn.; Catalog
1976.

RFR Corp., Hope, R.I.; "Chemical Standards for Air-Water-
Industry-Froods" (1975).

“Analytical Reference Standards and Supplemental Data for
Pesticides and Other Selected Organic Compounds", EPA-
660/9-76-012 (May 1976), Health Effects Research Laboratory,
Environmental Toxicology Division, Research Triangle Park,
NC. A sample order blank for standards and the above
publication are attached.

Columbia Organics Catalog A-7, Columbia, $.C. (1975).

Tridom Chemical Inc., Hauttauge, N.Y¥., Catalog No. 1
(1976). .


Separatory Funnel Extraction
Acid (Phenols) Extraction...
Emulsions ..... 2. + ee ee
Continuous Extraction ...
Blank Extraction. ...... es
“pesticides . 2... 2.5.00 ee
GC-MS Analysis . .... 2... 2 ee ee
Base-Neutral . 1... 2 ee ee
Acid 2... 1 ee ee eee ewe
Quality Assurance ..... 2. 2 eee

Reporting of Data ... 2... 2 eee
METALS «2 1 ee eee ew ee tw ee we

Sample Preparation ........4.-.
Apparatus ...- 2.2 se ee eae
Procedure . 2. 2 2 ee ee ee eee
Quality Assurance . . 2... . e's ee

Data Reporting ......-+.-.4.4-ee-.

CYANIDES 2. 2 ee ee ew we ew eee eee
Sample Preparation ......+.4.s4e-.
Sample Procedure... 2... 2. ee. se
Quality Assurance . ......2.-

Reporting of Data ... 2... ee ee

17
18
19
20
20
21
23
23
25
29

230

43

43
44
44
47
48

49
49
49

49
49


- 40 -

Table VI

(continued)

Standards not available: as of 2/8/77

Nenitrosodi-n-propylamine

4-chlorophenyl phenyl ether

TCDD

endrin aldehyde

N-nitrosodimethylamine
3,3'-dichlorobenzidine
bis(chloromethyl)ether (unstable in water)

Standards that would not chromatograph:

4,6-dinitro-o-cresol
4-nitrophenol
2,4-dinitrophenol

Standards vielding a range of peaks:

Rr?

PCB-1242 0.93-1.24
PCB-1254 1.18-1.41
toxaphene 1.22-1.47

chlordane 1.14-1.37


- 38 -

Table VI. ELUTION ORDER OF MOST OF THE SEMIVOLATILE
PRIORITY POLLUTANTS ON 1% $P2250* (continued)

Compound rere ?c
2,6-dinitrotoluene 0.93
1,2-diphenylhyérazine 0.96
2,4-dinitrotoluene 0.98
N-nitrosodiphenylamine 0.99
hexachlorobenzene 1.00
4-bromophenyl phenyl ether 1.01
e-BHC 1.02
~BEC 1.o9F
phenanthrene 1.09%
anthracene 1.09
dimethyl phthalate 1.10
pentachlorophenol 1.11f
B-BHC 1.12
aldrin 1.14
diethyl phthalate 1.15
heptachlor 1.15
heptachlor epoxide 1.23
£luorenthene 1.23
e~endosuifan 1.24
dieldrin 1.28:
4,4'=DDE 1.30
pyrene 1.30
di-n-butyl phthalate 1.31
4,4'=DDD (p,p'-TDE) 1.33,
4,4'--DDT 1.387
endosulfan sulfate 1.41°
endrin 1.41
benzidine "13a"
butyl benzyl phthalate 1.46

chrysene 1.46


ca 63 -
APPENDIX IIT

.—_—____- COLLECTION_OF. SAMPLES_FGR SCREENING ANALYSES

The initial characterization (screening) of the varied industrial
discharges covered by this program will be made on an analysis of
a composite effluent sample. Any scheme for collecting a
composite sample is, in effect a method for mechanically
integrating to chtain average characteristics of a discharge.
Quring the screening phase the sample composite can be used to
determine the average characteristics which would be
representative of that discharge. Simple composite samples are
those that are made up ef a series ef aligucts of constant volume
collected at regular time intervals in a single container. Some
Situations may require flcw or time preportional sampling, this
determination will be made by the individual project officer
after considering his specific industrial catagory.

The determination of compositing period 24, 48 or 72 hours will .
be made on a case by case basis. The duration of compositing
will depend on the type of sample being coliected, the type of
facility being samcled and the time varying characteristics of
the discharge. The rate of change of flow and other
characteristics of the discharge and the accuracy required will
also influence the determination of the compositing period. For
‘example longer cempesiting periods would be warranted when less
stable unit process operations are being sampled.

Collection of Samples

“L. Collection of Composite Samples for Licuid-Licutd Extraction

Collect a representative composite sample. The maximum time
interval between aliquot samples shall be no longer than 30
minutes. The minimum aliquot size shall be 100 mi. The
sample must be collected with an automatic sempler using the
equipment and methods outlined below. Minimum compcsite
volume must be 2 1/2 gallons.

Automatic Sample Collection

Sampler - A peristaltic puma automatic sampler with
timer and a single glass cempositing jug is required. The 2
1/2 ~ 3 gallon compositing bottle must be glass and cleaned


-8-
attach the column exit to the detector. Adjust the helium
flow rate through the column to 33 ml/minute. Allow the
column to flush with helium for ten minutes at room tempera-
ture, then program the oven from room temperature to 1909¢ at

4°c/minute. Maintain the oven at 190°C overnight (16 hours).

" wandle the column with extreme care once it has been
conditioned because the Carbopack is fragile and easily frac-
tured. Once fractured, active sites are exposed resulting in
poor peak geometry (loss of theoretical plates) . Recondition-
ing, generally, revitalizes the analytical column. Once
properly conditioned, the precolumn may be removed. The re-
tention data listed in Table I was collected with the pre-

column in the system.

Quality Assurance - The analysis of blanks is most
important in the purge and trap technicue since the purging
device and the trap can be contaminated by residues from
very concentrated samples or by vapors in the laboratory. Pre-
pare blanks by filling a sample bottle with low-organic water
(blank water) that has been prepared by passing distilled
water through a pretested activated carbon column. Blanks
should be sealed, stored at 4°C, and analyzed with each group

‘of samples.

After each sample analysis, thoroughly, flush the purg-
ing device with blank water and bake out the system. Sub-

sequently, analyze a sample blank (one that has been transported


- 50 -

Phenols

Sample Preparation

Distill all samples prior to determination of phenols.
Use the procedure in "Standard Methods for the Examination of

Water and Wastewater,” 14th edition, 1975, p. 576 (Reference 10).

Procedure

Use method 510 for phenols in Appendix X, pages 577-580
and 580-581. Use method 510B for samples that contain less
than 1 mg/l of phenol. Use method 510C for samples that contain
more than 1 mg/l of phenol.

Quality Assurance

Demonstrate quantitative recovery with each distillation
apparatus by comparing distilled standards to non-distilled
standards. Each day distill, at least, one standard to con-

firm the distillation efficiency and purity of reagents.

Run duplicate and dosed sample analyses on at least 15%
of the samples analyzed for phenol. Establish and confirm

quality control limits as describec in Reference 9.

Reporting of Data
Report phenol concentrations as follows:
Method 510B to the nearest ug/l.
Methed 510C - when less than 1.0 ug/l to the nearest
0.01 mg; 1.0 mg/l and above to two significent figures.
Report all quality control data when reporting results

of sample analysis.


- 56 -
Appendix II__

Possible Sources for Some Priority Pollutant Standards

(Continued)
Source of

Compound : Standard?
Chlorinated phenols (other than those listed

elsewhere; includes trichlorophencls and

chlorinated cresols)
2,4,6-trichlorophenol AL p. 712
p-chloro-m-cresol TCI p. 102
chloroform (trichloromethane) Bp. 92
2-chlorephenol AL p. 187
DDT and metabolites
4,4°-DDT. HERL $1920
4,4'-DDE . HERL #1860
4,4'=DDD (p,p'-TDz) HERL $1780
Dichlorobenzenes (1,2-;1,3-; and 1,4-

dichlorobenzenes)
1,2-dichlorobenzene AL p. "258
.1,3-dichlorobenzene AL p. 258
1,4-dichlorobenzene AL p. 258
Dichlorobenzidine
3,3'-dichlorobenzidine? CPL p. 81
Dichloroethvlenes (1,1-dichloroethylene and

72-aichLloroethylene)

1,1-dichloroethylene AL p. 746
1,2-trans-dichloroethylene AL p. 262
2,4-dichlorophenol AL p. 265
Dichloropropane and dichloropropene
1,2~dichloropropane . AL p. 267
1,3-dichloropropylene (1,3-dichloropropene) AL p. 267
2,4-dimethylphenol AL p. 323
Dinitrotoluene
2,4-dinitrotoluene PB p. 180
2,6-dinitrotoluene PB p. 180

1,2-diphenylhydzazine AL p. 333


- 10 -

Calibration of the gas chromatography-mess spectrometry
(GC-MS) system - Evaluate the system performance each day
that it is to be used for the analysis of samples or blanks.
Inject a sample of 20 nanograms of decalfuorotriphenyl-

phosphine (a)

and plot the mass spectrum. The criteria in
Reference 2 must be met and all plots from the performance
evaluation, documented and retained as proof of valid

performance.

Analyze the 20 ug/l standard to demonstrate instrument

performance for these compounds.

Qualitative and Quantitative Determination - The char-
acteristic masses or mass ranges listed in Table II of this
section are used for qualitative and quantitative determination
of volatile priority pollutants. They are used to obtain an
extracted ion curzsent profile (EICP) (e) for each compound.

For very low concentrations, the same masses may be used for
selected ion monitoring (SIM) (£) . The primary ions to be used
to quantify each compound are also listed. If the sample pro-
duces an interference for the primary ion, use a secondary

ion to quantify.

(d) Available from PCR, Inc., Gainesville, FL.

(e) EICP is the reduction of mass spectrometric data
acquired by continuous, repetitive measurement of
spectra by plotting the change in relative abundance
of one or several ions as a function of time.

(£) SIM is the use of a mass spectrometer as a substance
selective detector by measuring the mass spectrometric
response at one or several characteristic masses in
real time.


CONTENTS
ORGANICS BY PURGE AND TRAP - GAS CHROMATOGRAPHY .....

Scope 2. 6 6 ewe ee ee ee ee ee ee te ee
Special Apparatus and Materials .........--.
Gas Chromatographic Column Materials... .....
Procedure . 2. 1 2 ee ee ee ee ee eee we
Preparation of Standards .......4.240+66
Preliminary Treatment of Sample ........
Purging and Trapping Procedure ........
GC-MS Determination... 2... 2. ee ee eee
Purge Parameters ....... tea o

Gas Chromatographic Parameters ......

Mass Spectrometer Parameters .......

Quality Assurance... 1... 2. ee ee ee ee
Precision. . 2... 2 ee eee ee eee
Calibration of GC-MS System .......
Qualitative’ and Quantitative Determination ..
Reporting of Data ... 2... 2 ee ee eee wwe

Direct Aqueous Injection Gas Chromatography ....
ORGANICS BY LIQUID-LIQUID EXTRACTION - GAS CHROMATOGRAPHY

Scope . 2... 2 ee eee eee ee

Special Apparatus and Materials ........4..
Procedure . 2. 6 wee eee ee ee ee ee
Base-Neutral Extraction. .........04

oovwtr ya Nn Dn ® FY WwW NY DN KB

PrP FP FB
YP Fo Oo

16

16
16
1s
17


-31-

Type - 9 track, 800 BPI, 2400 foot reels
Record length - 80

Block Size - <4000 (specify)

Code - EBCDIC

An acceptable data format would have the first two records
containing the sample identification. Subsequent records con-
tain eight mass-intensity pairs, each of which is 10 characters
long. Each mass and each intensity is 5 characters long and
left justified.’ At the end of each spectrum in a sample run,
the last mass-intensity pair is blank to denote the end of the
spectrum. When all data’ for the run is on the tape, an end-
of-file mark should be written. The next sample run can ‘then
be entered. One example is:

2 Records:Sample 1 identification

N Records:Spectrum 1 of sample, last mass-intensity

pair is blank to denote end of spectrum
M. Records:Spectrum 2 of sample, last mass-intensity

pair is blank to denote end of spectrum

L Records:Spectrum N of sample, last mass-intensity
pair is blank to denote end of spectrum

END OF FILE .
2 Records:Sample 2 identification

etc.


-19 -

extract with 200 x 100 x 100 ml portions of distilled-in-
glass methylene chloride. (Note that only 200 ml is used

for the first extraction). Proceed as described for the base-
neutral extract, including the addition of the internal
standard.

“Emulsions - The recovery of 85% of the added solvent
will constitute a working definition of a broken emulsion.
(You may correct the recovery of the first portion for water
solubility of methylene chloride.) Any technique that meets
this criteria is acceptable. Among techniques that have been
tried on these samples with fair success are:

1. Centrifugation of the emulsion layer after removel
of any separated solvent.

2. Passage of the emulsion through a column plugged
with a ball of methylene chloride-wet glass wool.
The solvent used to wet the wool and to wash it
after the emulsion goes through must be measured
and subtracted from the total volume to determine
853 recovery.

3. Relative to labor, solvent is cheap. The addition
of excess solvent sometimes breaks weak emulsions.
You must remember to use excess solvent in the :
blanks also.

4. Let the emulsion stand for up to 24 hrs.

5. Draw off the small amount of free solvent that sep-

arates and slowly drip it back in the top of the


600R77006

FOREWORD

These guidelines for samoling and analysis of industrial wastes
have been prepared by the staf? of the Environmental Monitoring and
Support Laboratcry, at the request of the Effluent Guidelines OQivision,
Office of Watar and Hazardous Wastes, and with the coaperaticn of the
Environmental Research Laboratory, Athens, Georgia. The procedures -
represent the currant state-of-the-art but improvements are anticipated
as more experienca with a wide variety of industrial wastes is obtained.
Users of these methods are encouraged to identify problems encountered and
assist in updating the test procedures by contacting the Environmental

Monitoring and Support Laboratory, EPA, Cincinnati, Ohio 45268.


1.

- 43 -

Metals

Sample Preparation

With the exception of mercury, the metals to be deter-

mined may be divided into two groups as follow:

a) those metals which are to be first analyzed by
flame atomic absorption (AA), and, if not detected,
then analyzed by flameless AA--Be, Cd, Cr, Cu, Ni,
Pb and Zn,

b) those metals which are to be analyzed by flameless

AA only--Ag, As, Sb, Se, and Tl.

For flame AA analysis the sample should be prepared using
the procedure as given in "Methods for Chemical Analyses of

Water and Wastes (1974)", 4.1.4, page 83 (Reference 7).

With the exception of antimony and beryllium, samples to
be analyzed by flameless AA should be prepared as an industrial
effluent as described in "Atomic Absorption Newsletter," 14,
page 111 (1975) (Reference 8). Note: Nickel nitrate should
be adéed only to those aliquots on which the analysis of
selenium and arsenic are to be accomplished. The sample prep-

aration procedure for antimony and beryllium analysis by flame-

less AA is the same procedure used for flame AA.

The sample preparation procedure to be used for mercury
analysis is that given in "Methods for Chemical Analysis of

Water and Wastes (1974)", 8.1, page 124 (Reference 7).


- 27 -

Table Ullists the 18 pesticides and PCB's that will be
confirmed by GC-MS using the sP2250 column. Chlordane,
toxaphene and the PCB's have retention ranges rather than
specific times due to their being multicomponent mixtures.
It is suggested that the first 14 materials be confirmed

exactly as the other base-neutral compounds.

The last four materials require special treatments. Chlor-
dane is expected to produce two main peaks within the retention
range given in which all three masses listed will maximize.
Toxaphene will produce several (5-15) peaks in which the masses
given will maximize within the retention time range. For the
PCB's each mass given corresponds to the molecular ion of PCB
isomers, e.g., 294 is tetrachlorobiphenyl. A specific mass plot
will show multiple peaks for each of these ions within the re-
tention time listed, but in general they will not maximize in
the same TIC peak. For these four materials in particular it
is necessary to also run a standard. Because GC-MS is only
being used for confirmation--and at its limit of detection-~-all
quantification will be done by EC-GC for the pesticides. The
methods for these four are not final and feedback from the

field to Dr. Shackelford is welcome.

When a compound has been identified, the quantification
of that compound will be based on the integrated area from
the specific ion plot of the first listed characteristic ion
in Tables Iv. and Vv. Quantification will be done by the

internal standard method using deuterated anthracene. Response


- 30

Table Vv. ‘Acid

Extractables

Characteristic
EI ions (Rel, Int.) -

l Limit of |
RRT Detection
Compound Name (2-nitrophenol) (ng)

- 2-chlorophenol 0.63 -100
phenol 0.66 100
2,4~dichlorophenol 0.96 100
2-nitrophenol 1,00 100
p-chloro-m-cresol 1.05 100
2,4,6-trichlorophenol 1.14 100
2,4-dimethylphenol 1.32 100
2,4-dinitrophenol 1.34 2 ug
4,6~-dinitro-o-cresol 1.42 2ug
4-nitrophenol 1.43 100
pentachlorophenol 1.64 100
deuterated anthracene (d10) 1.68 40

Column: 6' glass, 2 mm i.d.

Tenax GC - 60/89 mesh
100° - 300° @ ae mine

He @ 30 ml/min

128 (100), .64(54), 130(32)
94(100), 65(17), 66(19)
162(100), 164(58), 98(62)
139(100), 65(35), 109(8)
142(106), 107(80), 144 (32)
196(100), 198(92), 200(26)
122(100), 107(90), 121(55)
184(100), 63(59), 154(53)
198 (100), 182(35), 77(28)
65(100), 139(45), 109(72)
266 (100), 264(62), 268(63)
188(100), 94(19), 80(18)

CI ions

(Methane)

129, 131, 157
95, 123, 135

163,
140,
143,
197,
123,
185,
199,
140,
267,
189,

165,
168,
171,
199,
151,
213,
227,
168,
265,
217

167
122
183
201
163
225
239
122
269


- 22 -

If intractable emulsions are encountered that cannot
be broken as described in the GC-MS survey section, then a
fresh l-liter sample should be processed in a continuous
extractor using methylene chloride as the solvent as des-
cribed earlier. The methylene chloride will have to be
evaporated to a small volume and exchanged into hexane for
clean-up or EC-GC analysis. To do this, evaporate the methy-
lene chloride to 6 to 8 ml, cool, add 20 ml of hexane and
a@ fresh boiling stone and re-evaporate to the desired analy-

tical volume (5 ml or less).

Final storage and transport of sample extracts: After
analysis, the extracts of the base-neutrals, acids, blanks
and pesticides are to be sent to ERL, Athens, GA 30601,
ATIN: Dr. Walter Shackelford.

Each extract is to be.washed out of its container into
a1l0 ml glass ampul and brought to 5 ml +1 ml. Methylene
chloride is the solvent for the base-neutrals and acids,
hexane for pesticides. The ampuls are to be saaled ina
rounded-off, fire polished manner, i.e., no thin sharp peaks
of glass that are easily broken on handling and shipping.
After sealing the ampuls, put an indelible mark at the
solvent level. Securely attach a label or tag that. gives:

Type of fraction (base-neutral, etc.)
Industrial category

Name (of plant, city and state)


-6-

GC-MS data as soon as the GC-MS vacuum system has stabilized
(<1075 torr).

While the sample is being chromatographed, flush the
purging device with two 5-ml volumes of organic free water.
Then bake out the trap (vent to atmosphere) to minimize the
amount of water desorbed into the Gc-Ms system during the
succeeding injection step. [Note: If this bake out step
is omitted, the amount of water entering the GC-MS system
will progressively increase causing deterioration of and

potential shut down of the system.]

GC-MS Determination - Suggested analytical conditions
for determination of the priority pollutants amenable to
purge and trap, using the Tekmar LSC-1 and the computerized
Finnigan ‘1015 GC-MS are given below. Operating ‘conditions
vary from one system to another; therefore, each analyst

must optimize the conditions for his equipment.

Purge Parameters

Purge gas --delium, high purity grade

Purge time - 12 minutes

Purge flow - 40 ml/min.

Trap dimensions - 1/8 in. 0.D. (0.09 to 0.105 in. I.D.)
x 6 in. long

frap sorbent - Tenax-GC, 60/80 mesh (4 in.) plus Type 15
silica gel, 35/60 mesh (2 in.)

Desorption flow - 20 ml/min.

Desorption time - 4 min.

Desorption temperature - 130°C


- 58 -

Appendix II

Possible Sources for Some Priority Pollutant Standards

chrysene AN

P.

(Continued)
Source of
Compound Standard?
hexachlorocyclopentadiene AL p. 416
isophorone ‘AL p. 464
naphthalene AN p. 118
nitrobenzene AL p. 557
Nitrophenols (including 2,4-dinitrophenol and
nitrocresol)
2-nitrophenol AL p. 564
4-nitrophenol AL p. 364
2,4-dinitrophenol AL p. 332
4,6-dinitro-o-cresol TCI p. 188
Nitrosamines
N-nitrosodimethylamine? NI p. 173
N-nitrosodi-n-propylamine PB p. 310
N-nitrosodiphenylamine EA p. 159
pentachlorophenol AL p. 587
phenol AL p. 595
Phthalate esters
’ bis (2-ethylnexy!) phthalate CS p. 8
butyl benzyl phthalate cS p. 8
di-n-butyl phthalate cs p. 8
diethyl phthalate cs p. 8
dimethyl phthalate cs p. 8
Polychlorinated biphenyls (PCB's)
PCB-1242 (Aroc lor 1242) HERL #5703
PCB-1254 (Aroc lor 1254) HERL #5705
Palynuclear aromatic hydrocarbons (including
enzanthracenes, benzopyrenes, benzo-
fluoranthene, chrysenes, dibenzanthracenes,
and indenopyrenes)
1,2-benzanthracene AN p. 118
benzo[a]pyrene (3,4-benzopyrene) AN p. 118
3,4-benzofluoranthene NI
11,12-benzofluoranthene NI

118


2.

~- 44 -

, Apparatus

All samples are to be analyzed using an atomic absorption
spectrophotometer ecuipped with simultaneous background
capability. For arsenic, cadmium, antimony, selenium, thallium,
and zinc, either electrodeless discharge lamps or high intensity
hollow cathode lamps may be utilized. A heated graphite atom-
izer is to be used for all flameless AA work. A strip chart
recorder must be used as part of the readout system to detect

and avoid the inclusion of extraneous data.

Procedure

a) Flame AA - The procedures to be used are those
described in "Methods for Chemical Analysis of
Water and Wastes (1974) " (Reference 7) as referenced
in Table I below. Instructions as to when flame-
less AA is to be used are also included. For
those defined in the recommended procedures, the
instrument manufacturers recommendations are to
be followed. Background correction is to be used

on all analyses.


1)

2)

3)

4)

5)

6)

7)

- 46 -

Argon should be used as the purge gas in

all analyses.

Background correction and method of standard
addition must be used on all analyses.

A blank maximum temperature atomization, without
gas interrupt, should be accomplished before
each analytical determination.

The graphite tube or cuvette should be replaced
as suggested by the instrument manufacturer or
when contamination or lack of precision indicates
that replacement is necessary.

All disposable pipet tips should be cleaned
before use by soaking overnight in 5% redistilled
nitric acid, rinsed with tap and deionized

water, and dried.

The accuracy of the temperature indicator on the
heated graphite atomizer should be verified
before beginning any analytical work. This
should be done by plotting charring temperature
for a standard solution of a compound where the
volatilization temperature is known. The com-
pound used should have a volatilization tempez-
ature between 800 and 1200°C.

To insure that there is no loss from the acid
matrix prior to atomization, the optimum charring
temperature for each metal should be established
in the same manner (i.e., by plotting charzing
temperature versus atomization signal of standard

solution of each metal).


-9-

to and from the sampling site). If positive interferences
are noted, analyze a fresh laboratory sample of blank water.
If positive interference still occurs, repeat the laboratory
blank analysis. If interference persists, dismantle the
system, thoroughly, clean all parts that the sample, purge
gas.and carrier gas come into contact with and replace or

repack the sorbent trap and change purge and carrier gas. :

Precision - Determine the precision of the method by
dosing blank water with the compounds selected es internal
standards - bromochloromethane, 2-bromo-l-chloropropane, and
1,4-dichlorobutane - and running replicate analyses. These
compounds represent early, middle, and late eluters over the
range of the Consent Decree compounds and are not, themselves,
included on the list. Construct Quality Control charts from

the data obtained according to directions in Reference 9.

The sample matrix can affect the purging efficiencies
of individual compounds; therefore, each sample must be
dosed with the internal standards and analyzed in a manner
identical to the internal standards in blank water. When
the results of the dosed sample analyses show a deviation
greater than two sigma, repeat the dosed sample analyses.
If the deviation is again greater than two sigma, dose
another aliquot of the same sample with the compounds of
interest at approximately two times the measured values and
analyze. Calculate the recovery for the individual compounds

using these data.*

*See Reporting of Data Section, p. ll.