TD8975S25197
SAMPLING AND ANALYSIS PROCEDURES FOR
SCREENING OF INDUSTRIAL EFFLUENTS FOR PRIORITY POLLUTANTS
U. S. ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
. CINCINNATI, OEIO 45253
MARCH, 1977
Revised
APRIL, 1977
U.S. Environmental Protection Agency
Region 5 Library (PL-12J)
77 West Jackson Blvd., 12th Floor
Chicago, IL 60604-3590
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FOREWORD
These guidelines for sampling and analysis of industrial wastes
have been prepared by the staff of the Environmental Monitoring and
Support Laboratory, at the request of the Effluent Guidelines Division,
Office of Hater and Hazardous Wastes, and with the cooperation of the
Environmental Research Laboratory, Athens, Georgia. The procedures •
represent the current state-of-the-art but improvements are anticipated
as more experience 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 45253.
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CONTENTS
ORGANICS BY PURGE AND TRAP - GAS CHROMATOGRAPHY 1
Scope 1
Special Apparatus and Materials 2
Gas Chromatographic Column Materials 2
Procedure '.... 3
Preparation of Standards 3
Preliminary Treatment of Sample 4
Purging and Trapping Procedure 4
GC-MS Determination 6
Purge Parameters 6
Gas Chromatographic Parameters 7
Mass Spectrometer Parameters 7
Quality Assurance 3
Precision 9
Calibration of GC-MS System 10
Qualitative" and Quantitative Determination .... 10
Reporting of Data 11
Direct Aqueous Injection Gas Chromatography 11
ORGANICS 3Y LIQUID-LIQUID EXTRACTION - GAS CHROMATOGRAPHY . . 16
Scope 16
Special Apparatus and Materials 16
Procedure 16
Base-Neutral Extraction 17
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Separatory Funnel Extraction 17
Acid (Phenols) Extraction 18
Emulsions 19
Continuous Extraction 20
Blank Extraction . 20
" Pesticides 21
GC-MS Analysis 23
Base-Neutral 23
Acid 25
Quality Assurance 29
Reporting of Data .30
METALS 43
Sample Preparation 43
Apparatus 44
Procedure » 44
Quality Assurance . . . . . 47
Data Reporting 43
CYANIDES 49
Sample Preparation 49
Sample Procedure 49
.Quality Assurance 49
Reporting of Data 49
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PHENOLS 50
Sample Preparation 50
Procedure 50
Quality Assurance 50
Reporting of Data 50
REFERENCES 51
APPENDIX I 53
APPENDIX II 55
APPENDIX III 63
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Appendices
I. General Information
II. Possible Sources for Some Priority Pollutant Standards
III. Collection of Samples for Screening Analyses
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LIST OF TABLES
Table I. Elation Order of Volatile Priority Pollutants ... 12
Table II. Characteristic Ions of Volatile Organics 14
Table III. Pesticides 33
Table IV... Base-Neutral Extractables 34
Table V. Acid Extractables 36
Table VI. Elution Order of Most of the Semivolatile
Priority Pollutants 37
Table VII. Order of Elution for OV-17 SCOT Column 41
Table VIII. Metals 45
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Organics by Purge and Trap -
gas Chromatograohy
1. Scope
This method is designed to determine those "unambiguous
priority pollutants/" associated with the Consent Decree/ that
are amenable to the purge and trap method1 . 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/1.
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
method of choice. The gas chromatographic conditions selected
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for the purge and trap method are, generally, not suitable for
the determination of compounds eluting later than chlorobenzene.
2. Special Apparatus and Materials
Sample extraction apparatus (minimum requirements):
5-ml glass syringes with Luar-Lok - 3 each
2-way syringe valves (Teflon or Kel-F) - 3 each
8-inch, 20 gauge syringe needle - 2 each
5-ml glass, gas-tight syringe, pressure-lok
or equivalent - 1 each
Tekmar Liquid Sample Concentrator, model LSC-1
or equivalent. Includes a sorbent trap
consisting of 1/8 in. O.D. (0.09 to 0.105
in. I.D.) x S in. long stainless steel tube
packed with 4 inches of Tenax-GC (60/30 mesh
and 2 inches of Davison Type-15 silica gel
(35/60 mesh).
3. Gas Chromatocraphic Column Materials
Stainless steel tubing 1/8 in. O.D. (0.09 to 0.105 in.
I.D.) by 8 ft. long. Carbopack C (60/30 mesh) coated with
0.2% Carbowax 1500. Chromosorb-W (60-80 mesh) coated with
3% Carbowax 1500.
(a) Available from Precisian Sampling Corp., P.O. Box 15119,
Baton Rouge, LA 70815.
(b) Available from Tekmar Company, P.O. Box 37202,
Cincinnati, OH 45222.
(c) Available from Supelco, Suzrelco Park, Beliefonte, PA
16823. Stock No. 1-1826.
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4'. 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 stand-
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 9.3 ml of
methyl alcohol to 0.1 mg. Lower the syringe needle to about
f '
. 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. Stock standards of compounds which boil above room
temperature are generally stable for at least four weeks when
stored at 4°C.
[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 jroncentration of such materials.]
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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/ul containing each of the compounds to be determined.
Prepare a 20 ug/1 quality check sample from the 100 ng/jil
standard by dosing 20.0 yl 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-brcmo-l-chloropropane, and 1,4- .
dichlorofautane to 45 ml of organic free (blank 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 20-25°C.
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. Hemove
the plungers from two 5-ml syringes and attach a closed 2-way
syringe valve to each. Open the sample bottle and carefully
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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 so'rbed on the Tenax-silica gel trap at
room temperature (20-25°C).
While the. sample is being purged, cool the gas chromato-
v
graphic column oven to near room temperature (20-30°C). To •
t
do 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 130QC, 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 elutad. Begin collecting GC-MS
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GC-MS data as soon as the GC-MS vacuum system has stabilized
(
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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 a 1 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/rain.
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 17Q°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 - (-)IOO volts
Extractor voltage - 3 volts
Mass range - 20-27, 33-260 amu
Integration time/amu - 17 milliseconds
Samples/amu - 1
Gas Chromatographic Column Conditioning Procedure -
Attach the Carbowax 1500-Chromosorb end of the column to the
iinlet system of the gas chromatograph. Do not, at this time,
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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 190°C at
4°C/minute. Maintain the oven at 190°C overnight (16 hours).
Handle 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 technique 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
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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 as internal
standards - bromochloromethane, 2-bromo-l-chloropropane, and
1,4-dichlorofautane - 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. 11.
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Calibration of the gas chromatography-mass 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 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/1 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
(Q\
extracted ion current profile (EICP) for each compound.
For very low concentrations, the same masses may be used for
selected ion monitoring (SIX) . 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) SICP 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.
(f) 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.
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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)
(Area for standard) ,, - „_,,__.._
Concentration of standard (ug/l) * ug/1 of *******
5. Reporting o_f Data
Report all results to two significant figures or to the
nearest 10 ug/1- 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 "Organic^ 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.
6. 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/1 and above.
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Table I
Elution Order of Volatile Priority Pollutants
(a)
Compound
chlorome thane
dichlorodif luororae thane
bromomethane
vinyl chloride
chloroethane
methylene chloride
trichlorof luoromethane
1,1-dichloroethylene
bromochloroniethane (IS)
1 , 1-dichloroethane
trans-l,2-dichloroethylene
chloroform
KRT
0 . 152
0.172
0.181
0.186
0.204
0.292
0 . 372
0.380
0.457
0.469
0.493
0.557
Purging
Efficiency
(percent)
91
0
85
101
90
76
96
97
Purging
Efficiency
Modified
Method
(percent)
100
(c)
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Table I
Elution Order of Volatile Priority Pollutants
Compound
chloromethane
dichlorodifluoromethane
bromomethane
vinyl chloride
chloroethane
methylene chloride
trichlorofluoromethane
1,1-dichloroethylene
bromochloromethane(IS)
1,1-dichloroethane
trans-1,2-dichloroethylene
chloroform
I,2-dichloroethane
1,1,1-trichloroethane
carbon tetrachloride
bromodichloromethane
bis-chloromethy1 ether
1,2-dichloropropane
trans-1,3-dichloropropene
trichlcroethylene
dibromochloromethane
cis-1,3-dichloropropene
1,1,2-trichloroethane
benzene
2-chloroethylvinyl ether
2-bromo-l-chloropropane(IS)
bromoform
1,1,2,2-tetrachloroether.e
1,1,2,2-tetrachloroethar.e
RRT
(b)
Pxirging
Efficiency
(percent)
Purging
Efficiency
Modified
Method
(cercent)
0.152
0.172
0.181
0.136
0.204
0.292
0^372
0.330
0.457
0.469
0.493
0.557
0.600 '
0.672
0.634
0.750
0.760
0.318
0.847
0.867
0.931
0.913
0.913
0.937
0.992
1.000
1.115
1.252
1.231
91
0 100 (C)
85
101
90
76
96
97
83
89
92
95
98
94
87
92
0
92
90
39
37
85
88
no data
no data
92
71
33
53
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Table I (cont'd)
Compound
I,4-dichlorobutane(IS)
toluene
chlorobenzene
ethylbenzene
acrolain
acrylcnitrile
RRT
(b)
1.312
1.341
1.489
1.814
unknown
unknown
Purging
Efficiency
(percent)
74
no data
39
no data
12
no data
Purging
Efficiency
Modified
Method
(percent)
74
(e)
(a) 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 a 1 ft. long x 0.1 in. I.D.
column packed with Chromosorb W coated with 3% Carbowax
1500; carrier 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.
(b) Retention times relative to 2-bromo-l-chloropropane
with an absolute retention time of 829 seconds.
(c) No measurable recovery using standard purging and trap-
ping conditions. Under modified conditions, i.e.,
purging at 10 ml/min. for 12 min., recovery is 100%.
(d) 3is-chloromethyl ether has a very short half-life in
water and is not likely to be detected in water.
(e) Recovery 12% under standard purging conditions, i.e.,
room temperature, 30% at 55°C, and 74% at 95°C.
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Table II
Characteristic Ions of Volatile Organics
Compound
chloromethane
dichlorodifluoromethane
bromomethane
vinyl chloride
chloroethane
methylene chloride
trichiorofluoromethane
1,1-dichloroethylene
bromochloromethane(IS)
1,1-dichloroethane
trans-1,2-dichloroethylans
chloroform
1,2-dichloroethane
1,1,1-trichlcroethane
carbon tatrachloride
bromodichloromethane
bis-chloromethyl ether
• 1,2-dichloropropane
trans-1,3-dichloropropene
trichloroethylene
dibrcmochloromethane
cis-1,3-dichloropropene
El Ions (Relative
intensity)
Ion used to
ouantifv
50(100) ; 52(33)
85(100); 87(33) ;
101(13) ; 103(9)
94(100) ; 96(94)
62(100); 64(33)
64(100) ; 66(33)
49(100>;51(33) ;
84(861; 86(55)
101(100) ; 103(66)
61(100) ; 96(80) ; 98(53)
49(100) ; 130(88) ;
128(70); 51(33)
63(100) ; 65(33) ; 83(13) ;
85(8); 98(7) ; 100(4)
61(100); 96(90) ; 98(57)
83(100) ; 85(66)
62(100) ; 64(33) ;
93(23); 100(15)
98(100) ; 99(66) ;
117(17); 119(16)
117(100); 119(96); 121(30)
83(100) 85(66);
127(13) 129(17)
79(100) 81(33)
63(100) 65(33);
112(4) ; 114(3)
75(100) 77(33)
95(100) 97(66);
130(90) 132(85)
129(100) ; 127(73) ;
208(13) ; 206(10)
75(100) ; 77(33)
50
101
. 94
62
64
34
101
96
128
63
96
83
98
97
117
127
79
112
75
130
127
75
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Compound
1,1,2-trichloroethane
benzene
2-chloroethylvinyl ether
2-bromo-i-chloropropane(IS)
faromoform
1,1,2,2-tetrachloroethene
1,1,2,2-tetrachloroethane
1,4-dichlorobutane(IS)
toluene
chlorobenzene
ethylbenzane
acrolein
acrylonitrile
Table (cont'd)
SI Ions (Relative
intensity)
Ion used to
quantify
83(95) ; 85(60) ; 97(100)-;
99(63) ; 132(9); 134(8)
78(100)
63(95) ; 65(32) ; 106(18)
77(100) ; 79(33) ;156(5)
171(50) ;173 (100); 175(50);
250(4); 252(11); 254(11);
256(4)
129(64) ; 131(62) ;
164(73) ; 166(100)
83 (100) ; 85(66) ; 131(7) ;
133(7); 166(5) ; 168(6)
55(100) ; 90(30) ; 92(10)
91(100) ; 92(78)
112(100) ; 114(33)
91(100); 106(33)
26(49) ; -27(100);
55 («4) ; 56(83)
26(100) ; 51(32) ;
52(75) ; 53(99)
97
78
106
77
173
164
168
55
92
112
106 .
56
53
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T
Organics by Liquid-Liquid Extraction -
Gas Chromatography
1. Scope
.. This method is designed to determine those "unambiguous
priority pollutants" associated with the Consent Decree/ that
are solvent extractable and amenable to gas chrpraatography.
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.
2. Special Apparatus and Materials
Separatory funnels - 2 and 4-liter with Teflon stopcock
Continuous liquid-liquid extractors - any such apparatus
designed for use with solvents heavier than water
and having a capacity of 2 to 5-liters . Con-
necting joints and stopcocks must be of Teflon or
glass with no lubrication.
3. 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,
Catalogue. Z10, 157-5.
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a representative 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.] 1
Base-Neutral Extraction
Separatory Funnel Extraction -. Adjust the pH of the sample
with 6 N NaOH to 11 or greater. Use multirange pH paper for
the measurement. Serially extract with 250 x 100 x 100 ml
portions of dist'illed-in-glass methylene chloride. (About 40 ml
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 (X-D) evaporation (distillation). The sodium
sulfate should be prewashed in the column with methylene
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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 ul of 2 ug/yl d,Q-anthracene (per each
ml of extract). Mix thoroughly.
If 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 pE of the base-
neutral extracted water with 6 N HC1 to 2 or less. Serially
-------
- 19 -
«
extract with 200 x 100 x 100 ml portions of distilied-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
v
after .the emulsion goes through must be measured
and subtracted from the total volume to determine
85% 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
-------
- 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 evap-
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.
-------
- 21 -
Pesticides: These, compounds are to be analyzed by
EC-GC using the EPA nethcd published in the Federal Register,
Vol. 33, Number 125, Part II, pp. 17313-17323. (Friday,
June 29, 1973). One-liter rather than 100 ml is to be ex-
tracted. The solvent amounts given in the method and other
parameters remain 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 III.
s
If the pesticide sample has-been received in a 1-gal*
bottle, hand shake the bottle for 1 min. by the clock to evenly
suspend sediment. Pour the sample into a 1-liter graduated
.cylinder and measure the volume. Then transfer the sample
•
to a 2-liter separatory funnel and rinse the cylinder 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 from the original composite
bottle, homogeneously mix as described earlier and transfer
a 1-liter aliquot to a graduated cylinder, then transfer
to the separatory funnel with the aid of a glass funnel and
rinse the cylinder as above.
-------
- 22 -
If intractable emulsions are encountered that cannot
be broken as described in the GC-MS survey section/ then a
fresh 1-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-
leae 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 SRL, Athens, GA 30601,
ATTN: Dr. Walter Shackelford.
•
Each extract is to be washed out of its container into
a 10 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 sealed in a
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)
-------
- 23 -
Specific source or stage of treatment
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 com-
posite sample may be discarded.
4. GC-MS Analysis
Compounds to be analysed 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 under the following chromatographic conditions:
Column - S foot, 2.0 mm inside diameter, glass
Packing - 1% SP22SO on 100/120 mesh Supelcoport.
Program - hold 4 minutes 3 50°, program 50C-250°
3 8°/min., hold 20 minutes §260°
Injector - 275°
Separator - 273°
Carrier gas - He @ 30 ml/min
Injection size - >_2 ul
-------
- 24 -
Table IV lists the 49 base-neutral extractable compounds
in order of relative retention tines (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 2,3,7,3-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 each GC-MS run of a base-neutral
extract, the operator 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
Table 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 SP-2250
may be used. The eluticn order of OV-17 and 35-2250 are very
similar. Some specific data for OV-17 is given in Table VII.
The performance criteria for benzidine must still be met
-------
- 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, 60/30 mesh
Program - 180° - 300° (§ S°/min
Injector - 290°
Separator - 290°
Carrier Gas - He @ 30 ml/min
Injection size - >2 ul
Table V 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
utilising a jet separator for the GC effluent since membrane
separators lose sensitivity for light molecules and glass
frit separators inhibit the eluticn of polynuclear aromatics.
A computer system should be interfaced to the mass spectro-
meter to allow acquisition of continuous mass scans for the
duration of the chromatcgraphic program. The computer system
-------
- 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. Second, 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
fables III-V within t 20%.
An example of identifying a component is as follows:
It is known that hexachlorobenzene elutes from the SP2250
column at 19.4 minutes. Hexachlorobenzene has characteristic
mass ions at 234(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 13.4-20-.4
minutes is examined for the simultaneous peaking of the in-
tensities of these ions. If all three ions are present, the
ratio of the peak heights is checked to verify that it is
100:30:24 i 20%. If the three tests are successful, hexachloro-
benzene has been identified in the samcle.
-------
- 27 -
Table HIlists the 18 pesticides and PCB's that will be
confirmed by GC-MS using the SP225Q 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
PC3's each mass given corresponds to the molecular ion of PC3
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 SC-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 V. Quantification will be done by the
internal standard method using deuterated anthracene. Response
-------
- 28 -
9
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:
AT CH
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 in-v.
The concentration of a compound in the extract may now
be calculated using:
_ Ac x Ca
- x R
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.
-------
- 29 -
In samples that contain an inordinate number of inter-
ferences the chemical ionization (CI) mass spectrum may make
identification easier. In Tables iv and v characteristic
CI ions for most compounds are given. The use of chemical
ionization MS to support El 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 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 SF2250 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 analysed by solvent extraction
once each 20 working days and the results reported with other
analytical data.
The 1% SP22SO and Tenax GC column packings are available
by request to EPA contractors from Dr. Walter Shackelford, SPA,
Athens, GA.
(b) Available from PCS, Gainesville, FL
-------
- 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
SP2250 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. If
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/1 except in those cases listed in Tables iv-V
in which limits of detection are too high for analysis at this
level.
6. 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:
-------
- 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 ?ILE
2 Records:Sample 2 identification
etc.
-------
- 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
-------
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- 37 -
Table VI. ELOTION ORDER OF MOST OF TH2 SE2CVOIATILE
PRIORITY POLLUTANTS ON 1% SP2250a
Compound
1,3-dichlorobensene 0.35
2-chlorophenol 0.35e
1,4-dichlorobenzene 0.36
hexachloroethane 0.38
1,2-dichlorobenzene 0.39
bis(2-chloroisopropyl)ether 0.47
0-endosTilfan 0.51
2,4-dinathyl phenol 0.52e
2-nitrophanol 0.53e
2,4-dichlorophenol 0.53s
he xachlorobutadiene 0.55
1,2,4-trichlorobenzene 0.55
naphthalene 0.57
bis(2-chloroethyl)ether 0.61
hexachlorocyclopentadiene 0.64
nitrobenzene 0.64
phenol 0.67
bis(2-chloroethoxy) methane 0.68
2,4,6-trichlorophenol 0.71e
p-chloro-m-crasol 0.73
2-chloronaphthalene 0.76
acanaphthylene • 0.83
acenaphthane 0.86
isophorone 0.87
fluorene . 0.91
-------
- 38 -
Table VI. ELDTION ORDER OF MOST OF THE SEMIVOLATILE
PRIORITY POLLUT3JHTS ON 1% SP225Qa (Continued)
Compound
RRT13'
2,6-dinitrcrtoluene . 0.93
1,2-dipheny Ihydr azine 0.96
2,4-dinitrotoluene 0.98
N-nitrosodiphenylanine 0.99
hexachlorobenzene 1.00
4-broicopb.enyl phenyl ether 1.01
o-BHC . 1.02
Y-BHC 1.09?
phenanthrane . 1.09
anthracene '1.09
dimethyl phthalate 1.10
peatachlorophenol . 1.11
3-BHC 1.12
aldrin , 1.14
diethyl phthalate 1.15
heotachlor 1.15
heptadalor epoxide 1.23
fluoranthene 1.23
a-«ndosulfan 1.24_
dieldrin 1.28'-
4,4'-DDE 1.30
pyrena 1.30
di-n-butyl phthalate 1.31
4,4'-DDD (p,p'-TDE) 1.33
4,4'—DDT 1.33d
f
endosulfan sulfate 1.41
endrin 1.41
benzidine ^l.Ta"
butyl benzyl phthalate 1.46
chrysene 1.46
-------
- 39 -
Table VI. ELOTION OBDSR OF MOST OF THE S2MIVOLATILE
PRIOHITY POLLUTANTS ON 1% SP2250a (Continued)
. - -' - - Compound KFnr3fC
bis(2-ethylhexyl)phthalate 1.50
benzo{a)anthracene 1.54
benzo(b)fluoranthene 1.66
banzo (lc) fluoranthene 1.66
benzo(a)pyrene 1.73
indeno(l,2,3-cd)pyrene 2.07
dibenz o(a,h)anthracene 2.12
benzo(ghilperylene 2.12
a 1% SP-225Q on 100/120 mesh Supelcoport in a 6T x 2ima id
'glass colijinn; He i 30ml/min; Program: 50* for 4 roin,
then 8a/min to 260° and hold for 15 mn.
Relative to hexachlorobenzene at 19.4 min.
c 40ng gives 5-90% response on FID unless otherwise noted.
200ng required to obtain 5-90% response on FID.
e 2 ug required.
£
40 iig required.
-------
- 40 -
*
Table VI
(continued)
Standards not available; as of 2/8/77
N-nitrosodi-n-propylamine
4-chlorophenyl phenyl ether
TCDD
endria aldehyde
N-nitrosodiinethylamine
3 r3 ' -dichlorobenzidine
bis (chlororaethyl) ether (unstable' in water)
Standards that would not chromato graph :
4 ,6-dinitro-o-cresol
4-nitropheno 1
2 , 4-dinitrophenol
• *
Standards yielding a range of peaks:
PCB-1242 0.93-1.24
PCB-1254 1.18-1.41
toxaphene 1.22-1.47
chlordane 1.14-1.37
-------
- 41 -
Table VII. Order of Elution for
OV-17 SCOT Coluinn
Compound Spectrum Number
1,3-dichlorobenzene 134
1,4-dichlorobenzene 137
2-chlorophenol 141
1,2-dichlorobenzene 153
bis(2-chloroethyl)ether 163
phenol . 165
bis(2-chloroisopropy1)ether 173
hexachloroethane 178
nitrobenzene 194
2-nitrophenol 219
1,2,4-trichlorobenzene 234
2,4-diraethylphenol ' 240
naphthalene 240
2,4-dichlorophenol 244
hexachlorobutadiene 262 •
isophorone 272 .
p-chloro-ra-cresol 317
hexachlorocyclopentadiene 325
2,4,6-trichlorophenol . • 332
chlorqnaphthalene 339
2,4-dinitrotoluene 372
acenaphthylene 374
acenaphthene 390
dimethyIphthalate 397
fluorene - 434
diethylphthalate 447
N-nitrosodiphenylanine 447
2,6-dinitrotoluene 454
a-BHC ' 476
4-bromophenvl phenyl ether 478
Y-BHC " 487
hexachlorobenzene 490
8-3HC 506
phenanthrene 518
anthracene 518
di-n-butylphthalate • 583
aldrin " 592
fluoranthane ' 617
pyrene 634
DDE 659
DDD 664
endrin 688
dieldrin .688
DDT . 713
butyl benzyl phthalata 713
benzo(a)anthracene 748
chrysene 748
-------
- 42 -
Table VII. Continued
Compound Spectrum Kumber
bis(2-ethylhexyl)phthalate -804
benzo(a)pyrene 906
benzo(b}fluoranthene ' 970
benzo(k)fluoranthene 970
33 meter glass OV-17 SCOT column,
Program: 6Or 260 d 6 /minute
Number of 2.5 second scans up to point of elution.
-------
- 43 -
A. • Metals
1. 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 analysed 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 added only to those alicuots 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).
-------
•* • ' - 44 -
2. (Apparatus
All samples are to be analyzed using an atomic absorption
spectrophotometer equipped 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.
».
3. Procedure
a) name 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 follo'wed. Background correction is to be used
on all analyses.
-------
- 45 -
Table vin
Methods for Chemical
Analysis of Water and
Element Wastes, 1974* Comments
Be p. 99 . Analyze by flameless AA if
cone. <20 wg/1
Cd p. 101 Analyze by flameless AA if
cone. <20 ug/1
Cr p. 105 Use nitrous oxide-acetylene
flame for all analyses—analyze
by flameless AA if cone. <200 ug/1
Cut p. 108 Analyze by flameless AA if
cone. <50 ug/1
Ni p. 141 Analyze by flameless AA if
cone. <100 ug/1
Pb p. 112 Analyze by flameless AA if *
cone. <300 ug/1
Zn p. 155 Analyze by flameless AA if
cone. <20 ug/1
*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
N.
incorporated into the procedures:
-------
- 46 -
1) Argon should be used as the purge gas in
all analyses.
2) Background correction and method of standard
addition must be used on all analyses.
3) A blank maximum temperature atomization, without
gas interrupt, should be accomplished before
each analytical determination.
4) The graphite tube or cuvette should be replaced
as suggested by the instrxunent manufacturer or
when contamination or lack of precision indicates
that replacement is necessary.
5) All disposable pipet tips should be cleaned
before use by soaking overnight in 5% redistilled
nitric acid/ rinsed with tap and deionised
water, and dried.
6) 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 temper-
ature between 800 and 1200°C-
7) 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 charring
temperature versus atomization signal of standard
solution of each metal).
-------
- 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.
c) 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) To verify that the instrument is operating correctly
within the expected performance limits, an appropriate
standard should be included between every ten samples.
b) Spiked aliquots shall be analyzed with a frequency
of 15% of 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 of 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 absorbance in the
unspiZ
-------
- 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/1/ nearest ug; 10 ug/1 and above, two significant figures
-------
- 49 -
Cyanides
1. 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.
2. 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.
3. 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 and confirmed as described
in Chapter 6 of the "Analytical Quality Control
Handbook" (Reference 9).
4. Reporting or_ Data
Report cyanide concentrations as follows: Less than
1.0 mg/1, nearest 0.01 mg; 1.0 mg/1 and above, two significant
figures.
-------
- 50 -
Phenols
Samale 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),
2. 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/1 of phenol. Use method 5IOC for samples that contain
more than 1 mg/1 of phenol.
3. 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 described in Reference 9.
4. Reporting of Data
Report phenol concentrations as follows:
Method 5103 to the nearest yg/1.
Method 510C - when less than 1.0 ug/1 to the nearest
0.01 mg; 1.0 mg/1 and above to two significent figures.
Report all quality control data when reporting results
of samole analysis.
-------
- 51 -
REFERENCES
1. "Determining Volatile Organics at Microgram-per-Liter Levels
it
by Gas Chromatography, T. A. Bellar and J. J. Lichtenberg,
• Jour. AWWA, 66 ,739-744, Dec. 1974.
2. "Reference Compound to Calibrate Ion Abundance Measurements
it
in Gas Chromatography—Mass Spectrometry Systems, J. W.
Eichelberger, L. E. Harris and W. L. Budde, Anal. Chem. 47,
995-1GQO (1975).
3. ASTM Annual Standards - Water, part 31, Method D29Q8 "Standard
Recommended Practice for Measuring Water by Aqueous-Injection
.Gas Chromatography.n
4. ASTM Annual Standards - Water, part 31, Method D3371 "Tentative
Method of 'Test for Nitriles in Aqueous Solution by Gas Liquid
Chromatograph."
5. "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).
6. Federal Register, Volume 33, number 125, part II, Appendix II,
p. 17319', Friday, June 29, 1975, "Determination of Organo-•
chlorine Pesticides in Industrial Effluents,"
it "
7. Methods for Chemical Analysis of Water and Wastes (1974),
U.S. Environmental Protection Agency, Technology Transfer.
8. "Determining Selenium in Water, Wastewater, Sediment and Sludge
by Flameless Atomic Absorption Spectroscopy, T. D. Martin and
J. F. Kcpp, Atomic Absorption Newsletter, 14., 109-116 (1975).
-------
- 52 -
S. '"Handbook for Analytical Quality Control in Water and Waste-
• k
11
water Laboratories (1972), U.S. Environmental Protection
Agency, Technology Transfer.
10. "Standard Methods for' the Examination of Water and Waste-
water," 14th edition, 1975.
-------
- 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
over 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.
-------
- 54 -
APPENDIX I
•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 11 phenols of interest here do chromatograph on
the Tenax column cited, the chromatography is poor, particularly
for the nitrophenols. Two other columns have shown good response
for the acid extractables. SP2250 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,S-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.
-------
- 55 -
Appendix II
Possible Sources for Some Priority Pollutant Standards
Compound-
acenaphthene
acrolein
acrylonitrile
aldrin
dieldrin
benzene
benzidine1
carbon tetrachloride
chlordane (technical
(tetrachlorome thane )
mixture & metabolites)
Source of
Standard 2
AN p. 118
AL p. 18
AL p. 19
HERL §30
HERL 12380
B p. 154
RFR "
B o. "88
HSRL *1200
Chlorinated benzenes (other than dichlorobenzenes)
chlorobenzene
1,2,4-trichlorobenzene '
hexachlorobenzene
Chlorinated ethanes (including 1/2-
dichloroethane, 1,1,1-trichloroethane
and hexachloroethane)
1,2-dichloroethane
1,1,1-trichloroethane
hexachloroe thane
1,1-dichloroethane
1,1,2-trichloroethane
1,1,2,2-tetrachloroethane
chloroethane
Chloroalkyl ethers (chloroiaethyl, chloroethyl and
mixed ethers)
bis (chloromethyl) ether1
bis(2-chloroethyl) ether
2-chloroethyl vinyl ether
Chlorinated naphthalene
AL p. 165
AL p. 710
AL p. 416
AL p.
B p.
AL o.
PB p.
PB o.
PB a.
EA p.
261
309
416
142
383
372
53
RFR
AL p. 173
AL p. 174
2-chloronaphthalene
ICN p. 50
-------
- 56 -
Appendix II_ _
Possible Sources for Some Priority Pollutant Standards
(Continued)
Contpound
Source of
Standard2
Chlorinated phenols (other than those listed
elsewhere; includes trichlorophenols and
chlorinated cresols)
2,4,6-trichlorophenol
p-chloro-m-cresol
chloroform (trichloromethane)
2-chlorcphenol
DDT and metabolites
4,4' -DDT.
4,4'-DDE
4,4'-DDD (p,p'-TDE)
Dichlorobenzenes (1,2-;1,3-; and 1,4-
dichlorobenzenes)
1,2-dichlorobenzene
•1,3-dichlorobenzene
1,4-dichlorobenzene
Dichlorobenzidine
3,3*-dichlorobenzidinel
Dichloroethylenes (1,1-dichloroethylene and
1,2-dichloroethylene)
1,1-dichloroethylene
1,2-trans-dichloroethylene
2,4-dichlorophenol
Dichlorcpropane and dichloropropene
1,2-dichloropropane
1,3-dichloropropylene (1,3-dichloropropene)
2,4-dimethylphenol
Dini trotoluene
2,4-dinitrotoluene
2,6-dinitrotoluene
1,2-diphenylhydrazine
AL p. 712
TCI p. 102
B p. 92
AL p. 187
HEEL £1920
HERL naso
HERL $1780
AL p. 258
AL p. 253
AL D. 258
C?L p. 81
AL p. 746
AL n. 262
AL p. 265
AL p. 267
AL p. 267
AL p. 323
PB p. 130
PB p. 180
AL p. 333
-------
- 57 -
Appendix II _. .
Possible Sources for Some Priority Pollutant Standards
(Continued)
Compound
Source of
Standard2
Endosulfan and metabolites
a-endosulfan
B-endosulfan
endosulfan sulfate
Endrin and metabolites
endrin
endrin aldehyde
HEEL S3220
HEBL 13200
NI p. 45
HERL £3260
NI p. 147
ethylbenzene
fluoranthene
Haloethers (other than those listed 'elsewhere)
4-chlorophenyl phenyl ether (p-chloro-
diphenyl ether)
4-broraophenyl phenyl ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
Halomethanes (other than those listed elsewhere)
methylene chloride (dichloromethane)
methyl chloride (chloromethane)
methyl bonnide (bromomethane)
bromoform (tribromomethane)
dichlorobromomethane
trichlorofluoromethane
dichlorodifluoromethane
chlorcdibromomethane
Heptachlor and metabolites
heptachlor
heptachlor epoxide
hexachlorobutadiene
Eexachlorobyclohexane (all isomers)
a-BEC
8-BHC
Y-BHC (liridane)
5-BEG
B p. 161
AN p. 113
RFR p. 6*
ICN p. 37
PB
PB p. 62
PB p.
PB p.
PB p,
PB p.
CO p.
PB p.
PB p.
CO p.
276
277
276
73
16
358
142
27
HERL $3360
EERL 338SO
AL B. 416
HERL $620
HERL f
HERL =680
HERL =660
-------
- 58 -
Appendix II
Possible Sources for Some Priority Pollutant Standards
(Continued)
Source of
Compound Standard.2
hexachlorocyclopentadiene AL p. 416
isophorone 'AL p. 464
naphthalene . AN p. 118
nitrobenzene AL p. 557
Nitrophenols (including 2,4-dinitrophenol and
dinitrocresol)
2-nitrophenol . AL p. 564
4-nitrophenol AL p. 564
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-nitrosodiphenylainine EA p. 159
pentachlorophenol ' ' AL p. 587
phenol AL p. 595
Phthalate esters
bis(2-ethylhexyl) 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 S5705
PQlynuclear aromatic hydrocarbons (including
benzanthracenes, benzopyrenes, benzo-
fluoranthene, chrysenes, dibenzanthracenes,
and indenopyrenes)
1,2-benzanthracene AN p. 113
benzo[a]pyrene (3,4-benzopyrene) AN p. 118
3,4-benzofluoranthene NI
11,12-benzofluoranthene NI
chrysene AN p. 118
-------
- 59 -
Appendix n
Possible Sources for Soina Priority Pollutant Standards
(Continued)
Compound
Source of
Standard *
acenaphthylene
anthracene
1 , 12-benzoperylene
fluorene
phenanthrene
1,2:5 r 6-dibenzanthracene
indeno (l/2/3-C/D)pyrene
pyrene
AN
AIT
AN
AN
AIT
AIT
AN
AN
P-
P-
P-
P-
P-
P.
P.
P-
1
118
118
118
118
"118
118
118
2,3,7, 8-tetrachlorodibenzo-p-dio:d.n (TCDD)
tetrachloroethylene
toluene
toxaphene
trichloroethylene
vinyl chloride (chloroethylene)
1-bromodecane (possible internal standard)
1-bromodod'ecane (possible internal standard)
NI p
AL p
AL
HERL
AL p
PS p
174
680
p. 701
£6740
711
406
Footnotes-:
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 nay 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.
-------
- 60 -
Sourcas of Standards and Abbreviations
AL Aldrich Chemical Co., Milwaukee, Wise.; Catalog 1977-1978.
AN Analabs, Inc., North Haven, Conn.; Catalog 13 (June 1976).
3 J. T. Baker Chemical Co., Phillipsburgh, N.J.;
Catalog 750 (July 1975).
CS Chem-Service, West Chester, Pa.; Bulletin CS-1QO-8 (1975).
CPL Chemical Procurement Laboratories, College Point, N.Y.;
1975 catalog..
EA Eastman Kodak Co., Rochester, N.Y.; Catalog 43 (1975).
ICN KSX Rare & Fine Chemicals, Piainview, N.Y.; Catalog No. 10
(1975).
NI Nanogens International, P.O. Box 437, Freedom, CA -95019
"Nanogen Index" (1975).
P3 Pfaltz & Bauer Chemical Co., STamford, Conn.; Catalog
1976.
RFR RFR Corp., Hope, R.I.; "Chemical Standards for Air-Water-
Industry-Foods" (1975).
EERL "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.
CO Columbia Organics Catalog A.-7, Columbia, S.C. (1975) .
TCI Tridom Chemical Inc., Haut.tauge, N.Y.,'Catalog No. 1
(1976).
-------
- 61 -'
, • ENVIRONMENTAL TOXICOLOGY DIVISICS
HEALTH EFFECTS RESEASCK LA30RATORY
• •' . UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, North Carolina '27711
SUBJECT: Inde* of Pesticides Analytical Reference DA7£. j Ig76
Standards - Update of Mailing List
FROM- Health Effects Research Laboratory, STD, AC3,
Research Triangle Park, SC, U.S.A. 27711 (MD-69)
TQ. All Laboratory Facilities on our Mailing List
•
This copy of the 1976 revision of our pesticides reference standards
index was nailed to the address appearing qn our sailing list. As this
list is several years old, we are sure that a number of addresses have
changed and that sorae are probably no longer existent.
If you wish to resiain on our. sailing list to receive future updates
of this publication, would you be good enough to cotsplete the nail-back
.below, snip it off, and return it to us. Do_ not tear off the back cover
to return to the address shown.- ; If you have no use for this publication
but know of sone other individual within your organization who is con-
cerned with pesticides analysis, would you convey this index, along, with
the aailbaek, to that parson.
To: U. S. Environmental Protection Agency
Health Effects Research Laboratory Date
Environmental Toxicology Division
Research Triangle Park; NC, U.S.A. 27711 (1-03-69}
D
D
We wish to be retained on_your nailing list to receive future updates
of the Pesticides Standards Index. The address shown on the envelops
is entirely correct and requires no changes.
We have no interest in future updates of this publication-. Please
cancel us frost your mailing list.
i—[ We wish to be retained on your sailing list, but the address shown
on the envelope should be changed to read (print or type)
_Recipient
-------
- 62 -
RSQUSST FOR ANALYTICAL 3ST33SSCZ STANDARDS
TO: Quality Assurance Section
Environmental Toxicology Division,
EPA, EEKL, Research Triangle Park, NC 27711
MD-69
Date
Date Request Recd_
Shipment Date
Lab Code No.
Order Filled bv
DO NOT WRITS IN THIS SPAC2
The following reference standards are required for our progran:
Catalog Compound. U Catalog Compound
Code (Catalog Name) | Code (Catalog Name)
No. I No.
1
||
.
II
*
I* necessary, use back of sheet to complete list. Covering letter unnecessary
if this fora is completed in full.
. .Name and address of laboratory "
RecTiestor's Name (Print or type)
IMPORTANT:
1. The amount of each standard is restricted to ICO ag because of the scarcity
and expense of refining analytical grade materials.
2. Please return at once, the acknowledgement card enclosed with each shipment.
This provides the sole evidence of delivery of the shipment.
3. Do not request compounds not listed in the catalog. No others ara stocksd.
4. If a bottle appears to be empty, remove cap and examine interior of botzle
and cap. Certain highly viscous materials tend to collect in cap.
-------
- 63 - .
. • ' APPENDIX III
JJCQLLECTIONlOF.SAMPLES_FOR 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 obtain average characteristics of a discharge.
During 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 cf a series of alicucts of constant volume
collected at regular time intervals in a single container. Some
situations may require flew or time proportional sampling, this
determination will be mace by the individual project officer
after considering his specific industrial category.
The determination cf compositing period 24, 43 or 72 hours will .
be made on a case by case basis. The duration of compositing
will depend on the type of sample being collected, the type of
facility being sampled 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 tha determination of the compositing period. For
'example longer canpositing periods would be warranted when less
stable unit process operations are being sampled.
Collection' of Samales
1. Collection of Composite Samples for Liouid-LiQuid 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 ICO ml. The
sample must be collected with s.n automatic sampler using the
equipment and methods outlined below. Minimum composite
volume must be 2 1/2 gallons.
Automatic Sample Collection
Sampler - A peristaltic puma automatic sampler with
timer and a single glass compositing jug is required. The 2
•1/2-3 gallon compositing bottle must be glass and cleaned
-------
- 64 -
as outlined below. Mew unused tubing must be used for the
sampling line and for the pump for each individual outfall or
sample location. Vacuum type automatic samplers may be used
provided that the sample chambers are glass and that they are
cleaned after every use as outlined for glass composite
containers. Place the sampler or composite container in an
insulated chest and ice. ^?ai^ta^^ the sample at 4'C during
the compositing procedure. At the completion of the
compositing period seal the container with a teflon lined
cap. Place the container in an insulated shipping container,
ice, 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 is imperative that
adequate sample flew rate be maintained throughout the samole
train in order to affectively transport the solids. In .
horizontal runs, the velocity must exceed the scour velocity,
while in vertical runs the settling or the fall velocity must
be exceeded several times to assure adequate transport of
solids in the flow. The equipment used in sampling raw
discharges than must have a minimum intake velocity of 2 feet
per second. In the sampling of treated effluents just about
any ccrnnerically available automatic liquid sampler could be
used.
When more than one laboratory is involved in the
analysis of the various parameters, the sample should if at
all possible not be divided in the field but rather at the
contractors' laboratory. For purpose of this program the
composite will be divided into four parts, one part for
metals, analysis, one for pesticides and PC3's, one for GC/MS
compounds and one for the classic parameters.
Blend the composite sample to provide a homogeneous
mixture including a representative suspension of any solids
In the container. No specific method is required, hard
stirring with clean glass or teflon rods, mechanical paddles
or magnetic mixing with tsflon coated stirring bars may be
used. Metal mixing devices may not be used.
Ketals - Withdraw a well blended aliquot of the
composite sample. Using a glass funnel, rinse the sample
container with a small portion of the sample, then transfer
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- 65 -
250 - 500 ml of sample to the bottle. Do not add any
preservative to the sample just seal and prepare for
shipment. AlTsamples must be carefully identified using •
labeles supplied by EGO. 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 Laboratory
1819 W. Pershing Road
Chicago, Illinois 50SG9
Raw discharge or treated affluent
' NS 7002200
Location,
S4(TICl«f_
Tyo* Sjrrslt.
N
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Plasma only
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- 6'6 -
Field Blank Procedure for Automatic Samplers
Blank. Water - Blank water must be as free from organic
Interferences as 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 detergent water and thoroughly rinsed with tap water and
blank water prior to use. Further rinsing with inethylene
chloride is required when parts permit, i.e., are not susceptible
to dissolution by the solvent. (Mete: Tygon pl'astic tubing is a
source of phthalate ester contamination. Where its use is
required, i.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 sampling system as in intake lines. In the
field, pump two liters of blank water through the sampling line
and pump tubing and discard. Then pump three liters of blank •
water through the system and collect as a blank in a 1-gallon
sample bottle that has been prepared as described below. Seal
the bottle with a Teflon lined cap. Immediately ice the blank (4'
C) and maintain at (4*C) during the transport and storage prior
to analysis.
Composite Container - Prepare narrow-mouth glass sample
bottles for use by washing with hot detergent water and
thoroughly rinsing with tap water and blank water. Heat the
bottles at 4CCTC in a muffle-furnace or dry heat sterilizer for
30 minutes or alternatively, rinse with methylene chloride and
air dry at room temperature protected frcm atcrnspheric or other
sources of contamination. Caps for the bottles must be lined
with Teflon which has been solvent rinsed as above.
2« Collection of Grab Samples
Collect grab samples ( minimum of one per day) for the
analysis of phenol, cyanide, and volatile organics
(purgable). Collect samples from the raw process discharge,
the treated effluent, and the treated effluent after
chlorination, when chlorinaticn is practiced. It is
reconanended that the samples be collected frcm mid-channel
at mid-depth. 'Samples should be collected -at a turbulent,
well mixed section of the channel.
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- 67 -
Cyanfde (Total)
Container - Usa new one-liter plastic bottles that will
not contaminate the sample. Wash the bottles and caps with
hot water and thoroughly rinse with tap water and blank
water.
Collect a 1-litar 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 iodide-starch test paper
(Kl-starch paper); a blue color indicates the need for
treatment. Add ascrobic acid, a few crystals at a time,
until a drop of the sample produces no color on the indicator
paper. Then add an additional 0.5 g of ascorbic acid for
each liter of sample volume. Then add 2 ml of 10 N sodium '
hydroxide per liter of sample (pH > 12).
« *"*
Seal the sample bottle and place in an insulated chest
and ice (4*C). Seal the chest and ship to the analytical
laboratory. Maintain at 4*C during transoort and storage
keep out of direct light prior to analysis.
Phenols
Container - Use new one-liter glass bottles. Wash the bottle
and Teflon cap liner with hot water and thoroughly rinse with tap
watar and blank water.
Collect a 1-litar sample.
Preservation"- At the time of collection, acidify the sample
by addition of phospheric acid or sulfuric to pH 4, Note volume
of acid added on sample tag. Seal bottle, place in insulated
chest and ica (4*C). Seal chest and'ship to analytical
laboratory. Maintain at 4*C during transport and storage. Keep
cut of direct light prior to analysis.
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- 68" -
• Organlcs (Purge and. Trap Method]
Containers - Use 45 to 125 ml screw cap glass vials with
Teflon faced si 1 cone septa:
Vials(*)- Pierce 112074 or equivalent
SeptaSa'- Pierce' 112722 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, cool 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 condition until just prior to filling with black
water or sample.
M Available from Pierce, Inc. Box 117, Rockfcrd, II 61105.
Collect duplicates 45-125 ml samples each time samples are
collected. Two blank water samples, sealed in 45 ml vials, are
to accompany the sample bottles during shipmsnt to and from the
.sampling site. If preservation for residual chlorine is to be
used, collect four samples during each sampling period.' Two
should be preserved and two not preserved.' Two preserved and two
non-prsservsd blanks are to be provided.
Filling and Sealing Bottles - Slowly fill each container to
overflowing. Carefully set the container on a 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 Seen properly sealed, invert the sample and
lightly tap the lid on a solid surface. The absence of entrapped
air bubbles indicates a proper seal. If air bubbles are prasar.t,
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 chloroform and other haloforms
continues in such samples if they are not stabilized. Wasta
streams that have been treated with chlorine should be tasted an
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, > ~ /
• , . - - 69 ~
- -'"N,
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site to determine whether or net preservative is needed. If
preservatation is recuired, collect both preserved and non-
preserved samples. Wrap the samples with water proof packing
material, place in an insulated chest and ice at 4*C. Maintain
at 4*C during transport and storage prior to analysis.
3. Identification of Samples
ATI saniples and blanks must be carefully identified
using water proof labels and v/ater proof ink. Include the
following inforaation on the label: sample number, date and
hour of sampling, complete information as to source and
sampling p-oint, preservative added, if any, and name of
person co-tlacting the sample (include address and/cr phone
nunser).
U.S. Environmental Protection Agency
Region 5 Library (PL-12J)
77 West Jackson Blvd., 12th Roor
Chicago, IL 60604-3590
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