SAMPLING AND ANALYSIS PROCEDURES FOR
SCREENING OF INDUSTRIAL EFFLUENTS FOR PRIORITY POLLUTANTS
U. S. ENVIRONMENTAL PROTECTION AGENCY
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
..CINCINNATI, OHIO 452S3
MARCH, 1977
Revised
APRIL, 1977
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60OR77006
FOREWORD
These guidelines for sampling and analysis of industrial wastes
have been prepared by the staff of the Environmental Monitaring and
Support Laboratory, at the request of the Effluent Guidelines Division,
Office of Water 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 wfth 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 45263.
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CONTENTS
ORGANICS BY PURGE AND TRAP - GAS CHROMATOGRAPHY
.......
Scope
......e.......
. . .
. . . . . .
Spec.ial Apparatus and Materials
. . . .
. . . . .
Gas Chromatographic Column Materials.
Procedure
. . .
. . .
. . .
. . . . .
. . .
. . .
. . . .
Preparation of Standards
. . . . .
. . . . .
Preliminary Treatment of Sample.
. . .
. . .
..........
. . .
Purqing and Trappinq Procedure
GC-MS Determination.
. . .
. . .
. . .
. . .
Purqe Parameters.
........
. . .
Gas Chromatographic Parameters
Mass Spectrometer Parameters
. . .
. . .
Quality Assurance. .
. . .
. . . .
. . .
Precision. . .
. . . .
. . . . . .
. . .
Calibration of GC-MS System
. . . .
Qualitative" and Quantitative Determination
Reporting of Data
. . .
..........
. . .
. . . . . .
. . .
Direct Aqueous Injection Gas Chromatography
. . .
. . .
. . .
. . . . .
. . .
. . .
. . .
. . . . .
. . .
. . . . .
. . .
. . . . .
. . . .
ORGANICS BY LIQUID-LIQUID EXT~~CTION - GAS CHRO~ATOGRAPHY . .
Scope
. . .
..........
....e..
Special Apparatus ~~d Materials
. . .
. . . c .
Procedure
..............
. . .
. . . . . .
Base-Neutral Ext.=action.. . .
. . . .
. . . . . . .
. . . . .
. . . .
1
1
2
2
3
3
4
4
6
6
7
7
a
9
10
10
11
11
16
16
16
16
17
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Separatory Funnel Extraction
Acid
(Phenols)
Extraction
Emulsions
Continuous Extraction
Blank Extraction.
Pesticides
GC-MS Analysis
Base-Neutral
Acid
Quality Assurance
.
Reportinq of Data
METALS
Sample Preparation
Apparatus
Procedure
Quality Assurance
Data Reportinq
CYANIDES
Sample Preparation
Sample Procedure
~uality Assurance
Reportinq of Data
'.
17
18
19
20
20
21
23
23
2S
29
. ,30'
43
43
44
, .
44
47
48
49
49
.
49
49
49
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APPENDIX
II
.' .
50
50
50
50
. 50
51
53
55
63
PHENOLS
Sample
Preparation
Procedure
Quality Assurance
Repori:inq of
Data
..
REFERENCES
.
APPE~TD IX
I
APPENDIX
III
-------
II.
tII.
Appendices
I.
General Information
Possible Sources for Some ?riority Pollutant Standards
Collec~ion of Samples for Screening Analyses
-------
LIST OF TABLES
Table I.
Elution Order of Volatile Priority Pollutants
. - .
12
14
Table II.
Characteristic Ions of Volatile Organics.
. . . .
Table III.
Pesticides
. . . . . . .
. . . . e
. . .
. . . .
33
34
Table IV.-.
Table V.
Base-Neutral Extractables
. . . .
. . . . . . . .
Acid Extractables
. . . . . .
. . . CI
.......
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 ~ Purge and ~ -
Gas Chromatoarachv
- J
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 method (1). These compounds
are listed in Table I of this section.
It is a gas chromato-
graphic-mass spectrometric (GC-MSl 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
_effici~ntly recovered by this method and should be detercined
by direct aqueous injection GC-MS.
Direct aqueous injection
GC-MS is recommended for all compounds that exceed 1000 ~g/l.
The purge and "trap and t..~e liquid-liquid extraction methods
are complementary to one another.
There is an area of overlap
be~Neen the two -and some compounds may be recovered by ei~~er
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 l300C and lSOoC with a water solubility of
approximately two percent. When compounds are efficiently re-
~, oS -;
covered by both methods, the chromatography determined the
method of choice.
The gas chromatographic conditions selected
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- 2 -
for the purge and trap method are, generally, not suitable for
the determination of compounds eluting later than chlorobenzene.
2.
Special A~~aratus and Materials
Sample ~~traction apparatus (minimum requirements) :
5-ml glass syringes wi~~ Luer-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-10k(a)
or equivalent - 1 each
T~~r Liquid Sample Concentrator, model LSC-l(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).
3.
~ Chromatogra~hic Column Materials
Stainless steel tubing 1/8 in. O.D. (0.09 to 0.105 in.
I.D.) by 8 ft. long. Carbopack C (60/80 mesh) coated wi~~
0.2% Carbowax l500(c). Chromosorb-W (60-80 mesh) coated with
3% Carbowax 1500.
(a)
Available from Precision Sampling Corp., P.O. Box 15119,
Baton Rouge, LA 70815.
~)
Available from Tekmar Company, P.O. Box 37202,
Cincinnati, OH 45222.
(c)
Available from Supelco, Supelco Park, Bellefonte, PA
16823. Stock No. 1-1826.
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- 3--
4".
Procedure
Preparation of'Standards - Prepare standard stock solu-
tions (approximately 2 ~g/~l) by adding, from a 100 ~l 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 v.olumetric flask containing 9.8 ml of
me~yl alcohol to 0.1 mg.
Lower the syringe needle to about
5 mm above the methyl alcohol meniscus.
Slowlv inject the
standard into the £lask.
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 OOC.
Stock standards of compounds which boil above room
temperature are generally stable for at least four weeks when
stored at 40C.
[Safety Caution:
.
Because of the toxicity of most organo-
halides, primary dilutions must be prepared i~ a hood.
Fur-
ther, it is advisable to use an approved respirator when
handli~g high_concent=ation of such materials.]
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- 4 -
From the primary dilution prepare a secondary dilution
mixture in methyl alcohol 50 that 20.0 ~l of the standard,
diluted to 100.0 m1 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/~1 containing each of the compounds to be determined.
Prepare a 20 ~g/l quality check sample from the 100 ng/~l
standard by dosing 20.0 ~l into 100.0 m1 of organic free water.
Internal Standard Dosing Solution - From stock standard
solutions prepared as above, add a volume to give 1000 ~g each
of bromochloromethane, 2-bromo-l-chloropropane, and 1,4- .
dichlorobutane 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 bas~s.
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 20-250C.
Purging a~d 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 ~d attach a closed 2-way
syringe valve to each.
Open the sample bottle and carefully
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- 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 ~~e valve.
Fill
the second sy~inge in an identical manner from the same
sample bottle.
sis as needed.
Use the second syringe for a duplicate analy-
Open the syringe valve and introduce 5.0 ~l of
the internal standard mixture through the valve bore, then
close the valve.
Attach the S-inch needle to the syringe
valve and inject the sample into the 9urging 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 (20-250C).
While the. sample is being purged, cool the gas chroma to-
.
gra~hic column oven to near room temperature (20-300C).
do this, turn heater off and open column oven door.
To .
At the completion of the l2-minute purge time, inject
the sample into "the gas chromatograph by turning ~~e valve
to the desorb 90sition.
Bold in this position for four min-
utes while rapidly heating the trap oven to lSOoC, then return
the valve to the purge position, close the GC column oven
door, and rapidly heat ~~e GC oven to 600C.
Consider this
time zero and begin to collect retention data.
Rold at 600C
for four minutes, ~~en program at SO/minute to l700C and hold
I until all compounds have eluted.
Eegin collecting GC-MS
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- 6 -
GC-MS data as soon as the GC-MS vacuum syst~ has stabilized
«lO-S torr).
While the sample is being chromatographed, flush the
purging device with two S.-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 ~~e
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 condition~
for determination of the priority pollutants amenable to
)
purge and trap, using the Tekmar LSC-l and the computerized
Finnigan 101S 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 --Helium, high purity grade
Purge time - 12 minutes
Purge flow - 40 ml/min.
Trap dimensions - 1/8 in. O.D. (0.09 to O.lOS in. I.D.)
x 6 in. long
Trap sorbent - Tenax-GC, 60/80 mesh (4 in.) plus Type 1S
silica gel, 35/60 mesh (2 in.)
Desorption flow - 20 ml/min.
Desorption ti~e - 4 min.
DesorPtion temperature - lSOoC
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- 7 -
~ 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/min.
Oven temperature - Room temperature during trap desorp-
tion,
then rapidly heat to 600C, hold at 600C for four min-
utes, then program to 1700C at SO/minute.
Hold at 170°C for
12 cinutes or until all compounds have eluted.
Mass Spe~trometer 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 r~~ge - 20-27, 33-260 ~~u
Integration time/amu - 17 milliseconds
Samples/amu - 1
Gas Chromatographic Column Conditioning Procedure -
Attach the Carbowax l500-Chromosorb end of the column to the
inlet system of the gas chromatograph.
Do not, at this time,
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- 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 190o~ at
4oC/.minute.
Maintain the oven at 1900C 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 geometrj (loss of theoretical plates) .
Recondition-
ing, generally, revitalizes the analytical column.
properly conditioned, the precolumn may be removed.
Once
The re-
tention cata listed in Table I was collected with the pre-
column in the system.
Quality Assur~~ce - 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.
~nanks
should be sealed, stored at 4oC, and analyzed with each group
of samples.
After each sample analysis, thoroughly, flush the purg-
ing device wi~~ blank water and bake out the system.
Sub-
saquently, analyze a sample bl~~ (one that has been transpor~ed
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- 9 -
, to and from the sampling site) .
If positive interferences
are noted, analyze a fresh laboratory sample of bla~~ 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 wi~~ the compounds selected as 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 ~~e 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 ~~e internal standards and analyzed in a manner
identical to the internal standards in bla~~ water.
Waen
the results of the dosed sample ~~alyses 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 wit~ the compou-"1ds of
interest at approximately two times the measured values and
analyze.
Calculate ~~e recovery for the individual compounds
using these data.*
*See Reporting of Data Section, p. 11.
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- 10 -
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 (d) and plot the mass spectrum. The criteria in
Reference
2
must be met and all plots from the performance
evaluation, documente~ and retained as proof of valid
performance.
Analyze ~~e 20 ~g/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. ~hey are used to obtain an
.
extracted ion current profile (EICP) (e) for each compound.
For very low concentrations, the same masses may be used for
selected ion monitoring (SIM) (f). The primary ions to be used
to qu~~tify each compound are also listed.
If the s~~ple pro-
duces an interference for the primary ion, use a seconda.-y
ion to quantify.
Available from PCR, Inc., Gainesville, FL.
(d)
(e)
EICP is the reduction of mass s~ectrometric 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 ~~e 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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- 11 -
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 .
~nen positive responses are observed, prepare and
analyze a reference standard so that the standard response
closely approximates the sample response.
cent~ation in the sample as follows:
Calculate the con-
(Area for unknown)
(Area for standard)
Concentration of standard (~g/l) = ~g/l of unknown
5.
Reporting of Q!!!
Report all results to two significant figures or to the
nearest 10 ~g/l.
Report internal standard data to two signif-
icant figures.
As the analyses are completed, ~ransfer GC-MS data to
magnetic tape as described Under reporting of data in method
for':0E_9'anIcs by Liqui-d-Liquid Extraction -~- Gas- Chroma~ography."
Report all quality control (QC) data along with the
analytical results for the samples.
In addition, for~ard
all QC data to EMSL, Cincinnati.
6.
Direct Aaueous Injection Gas Chromatogra~hv
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.~~ese methods is 0.1
mq/l and above.
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- 12 -
Table I
E1u~ion Order of Vola~ile Priority Pollutants (a)
Purqing
Efficiency
Purqing Modified
RRTCb) Efficiency Me~hod
Com'Cound ( percent) (percent)
chlorome~hane 0.152 91
dichlorodifluoromethane 0.172 0 100Cc)
bromomethane 0.181 85
vinyl chloride 0.186 101
chloroe~hane 0.204 90
methylene chloride 0.292 76
trich1orofluorometh~~e 0.372 96
1,1-dichloroethy1ene 0.380 97
bromoch1oromethane(IS) 0.457 88
1,1-dich1oroe~hane 0.469 89
~rans-l,2-dichloroethylene 0.493 92
chloroform 0.557 9~
~,2-dich1oroethane 0.600 98
1,1,1-trich1oroe~hane 0.672 94
carbon ~e~rachloride 0.684 87
bromodich1oromethane 0.750 92
bis-ch1oromethy1 ether(d) 0.760 0
1,2-dich1oroprop~e 0.818 92
trans-l,3-dich1oropropene 0.847 90
t=ichlcroethy1ene 0.867 89
dibromoch1oromethane 0.931 87
cis-1,3-dich1oropropene 0.913 85
1,1,2-trichloroe~~ane 0.913 88
benzene 0.937 no data
2-chloroethy1vinyl e~~er 0.992 no data
2-bromo-l-ch1oropropane(IS) 1. 000 92
bromoform 1.115 71
1,1,2,2-tet=achloroethene 1. 262 88
1,1,2,2-tetrach1oroethane 1. 281 58
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- 13 -
Table I (cont' d)
Purging
Efficiency
Purging Modified
RRT(b) Efficiency Method
Comcound (percen t) (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)
acrylonit=ile 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 wi~~ Carbo pack C (60/80 mesh), coated wi~~ 0.2%
Carbowax lSOO; preceeded by a 1 ft. long x 0.1 in. I.D.
column packed with Chromosorb W coated with 3% Carbowax
lSOO; carrie= flow - 40 ml/min.; oven temperature -
initial 600C held for 3 min., programmed aOC/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 tL~es relative to 2-bromo-l-chloropropane
wi~~ ~~ absolute retention time of 829 seconds.
No measurable recovery using standard purging and trap-
ping conditions. Under modified conditions, i.e.,
purging at io ml/rnin. 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% ~~der st~~dard purging conditions,
room temperature, 30% at 5SoC, and 74% at 9SoC.
i.e. ,
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- 14 -
Table II
Characteristic Ions of Volatile Organics
Com'Qound
chloromethane
dichlorodifluoromethane
bromomethane
vinyl chloride
chloroethane
methylene chloride
trichlorofluoromethane
l,l-dichloroethylene
bromochloromethane(IS)
1,1-dich1oroethane
trans-l,2-dic~loroethylene
chloroform
1,2-dichloroethane
1, 1, I-trichloroethane
carbon tetrachloride
bromodichloromethane .
bis-chloromethyl ether
'1,2-dichloropropane
trans-l,3-dich1oropropene
trichloroethylene
dibromochloromethane
cis-l,3-dichloropropene
EI Ions (Relative
intensity)
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(86~; 86(55)
101(100); 103(66)
61(100); 96(80); 98(53)
49 (10 0'); 13 0 (8 8) ;
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);
98 (2 3); ~ 00 (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 (78) ;
208(13); 206(10)
75 (100); 77 (33)
Ion used to
auantifv
50
101
94
62
64
84
101
96
128
63
96
83
98
97
117
127
79
112
75
130
127
75
-------
Com'Cound
1,1,2-trichloroethane
benzene
2-chloroethy1viny1 ether
2-bromo-i~chloropropane(IS}
bromoform
1, 1, 2, 2-tetrach1oroethene
1,l,2,2-tetrach1oroethane
l,4-dich1cirocutane(IS}
toluene
ch1orobenzene
ethy1benzene
. acrolein
aCr'j1oni tri1e
- 15 -
Table (cont'd)
EI Ions (Relative
intensity)
Ion used to
cruantifv
.
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 (78); 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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- 16 -
Organics by Liquid-Liquid Extraction -
Gas Chromatography
1.
Scope
..This method is designed to determine those nunambiguo~s
priority pollutants" associated with the Consent Decree, that
are solvent extractable and ~enable to gas ch~omatography.
These compounds are listed in Tables III to V 0: 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 ~~e industrial effluent study.
Pesticides
are initially d~termined by electron capture-gas chromatography
.
and, qualitati~ely, confirmed by mass spectrometry-
2.
Special A~paratus and Materials
,Separatory funnels - 2 and 4-liter with Teflon stopcock
Continuous iiquid-liquid extractors - any such apparatus
designed for use with solvents heavier than water
and having a capacity of 2 to 5-1itersCa) .
Con-
necting joints and stopcocks must be of Teflon or
glass with no lubrication.
3.
Procedure
Sample Preparation for GC-MS Survey - Blend ~~e co~-
posite sample to provide a homogeneous mixture including
Ca)
Available from Aldrich C~emical Co., Milwa~~ee, W!,
Catalog No. ZlO, 157-5.
-------
- Ii -
a representative portion of the suspen~ed solids that are
present.
No specific method is required but a motor driven
mechanical stirrer wi~~ a p~opeller type blade is suggested.
Stirri~g 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 vo 1 urne .
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 11 or greater.
Use multirange pH paper for
the measurement.
Serially extract with 250 x 100 x 100 ml
portions of distllled-in-glass methylene chloride.
(.Jl.bout 40 ml
of the first 250 ml portion will dissolve in the s~~ple and not
be recovered.)
Shake each extract for at least 2 min by ~~e
clock.
Dry and filter the solve~t extract by passing it ~~rough
a short cDlumn of sodium sulfate.
Concentrate the solvent by
Kuderna-Danish (K-D) evaporation (distillation).
The sodium
sulfate should be prewashed in the column with me~~yler.e
-------
- 18 -
chloride.
[Note:
Check sodium sulfate blank and, if
necessary, heat in an oven at 5000C for 2 hours to remove
interfering organics.]
After drying the extract, rinse the
sodium sulfate wi~~ 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 col~~ 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 an4 carefully evaporate to 1.0 ml
or when active distillation ceases.
Remove ~~e micro-Snyder
column and carefully evaporate to 1.0 ml or when active dis-
tillation ceases.
Remove the micro-Snyder column and add ~~e
internal standard:
10 ~l of 2 ~g/~l dlO-anthracene (per each
ml of extract) .
Mix thoroughly.
If it is to be overnight or longer before the extract is
r~~ by GC-MS, transfer it from the K-D ampul with a disposable
pipet to a solvent tight container.
The recommended container
is a st~~dard 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 mon~~s if ca?S 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) ?xtraction - Adjust ~~e pH of the base-
neutral extracted water with 6 N ECl to 2 or less.
Serially
-------
- 19 -
extract with 200 x 100 x 100 ml portions of distilled-in-
glass methylene chloride.
for the first extraction) .
(Note that only 200 ml is used
Proceed as described for the base-
neutral extract, including the a~dition of the internal
standard.
.0 Emulsions - The recovery of 85% of the added solvent
./
will constitute a working ~efinition of a broken emulsion.
.
(You may correct the recovery of the first portion for water
solubility of methylene chloride.)
Any tec~~ique 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
2.
of any separate~ solvent.
Passage of the emulsion through a column plugge~
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 deter~ne
85% recovery.
3.
Relative to labor, solvent is cheap.
The addition
of excess solvent sometimes breaks we~k emulsions.
You must remember to use excess solvent in ~~e
blanks also.
4.
s.
Let the emulsion stand for up to 24 hrs.
Draw off the small amount of f:=ee 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 wi~~ a fresh aliquot of sample and extract by
continuous extraction.
Adjust the pH of the sample as appropriate, pour into
~~e extractor, and extract for 24 hours.
When extracting a
2-liter sample, using the suggestec equipment, two liters of
bl~~~ 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 lite=s of bl~~ ~ill always be available.
When it is,
proceed to process it as the corresponding sample was done:
Include ~~y emulsion bre~~ing steps that used glass wool,
excess solvent or additional chemicals.
If less ~~an 2 liters
is available, measure the blank and bring it to volume with
distilled water.
On analysis m~~e the necessary quantita-
tive corrections.
-------
- 21 -
Pesticides:
These, compounds are to be analyzed by
EC-GC usL~g the EPA method published in the Federal Register,
Vol. 38, Number 125, Part II, pp. 17318-17323.
(Friday,
June 29, 1973).
One-liter rather than 100 ml is to be ex-
1:.racted.
The solvent amounts given in the method and other
par~ters r~~ain unchanged.
If pesticides are found by EC,
the e~~act is to be carefully evaporated (clean airstream)
~o 0.5 m1 and sent for GC-MS confirmation.
The compounds to be analyzed by EC-GC are listed in
Table II!.
...
If the pe~ticide sample has-been receLved ~ a l-ga~~
,
bottle, hand sh~
-------
- 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
evap?rated to a small volume and exchanged into hexane for
clean-up or EC-GC ~~alysis.
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,
ATTN:
Dr. Walter Shackeiford.
Each extract is to be washed ou~ of its container into
a 10 ml glass ampul and brought to 5 m1 t 1 ml.
Me~~ylene
chloride is ~~e solvent for ~~e 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 pe~
-------
- 23 -
Specific source or stage of t=aa~~ent
Date sampled
Da't:e sealed
Name of contractor and analytical laboratorI
Wrap 1:he ampuls in packi.I1g material to prevent breakage
and'mail or ship them postpaid. at ambient temperature.
When
the samples are safely in ~puls, the remainder of the com-
posite sacple may be discar~ed.
4.
GC-MS Analvsis
Compo~4ds to be analyzed by GC-MS alone fall into ~~o
,...-'
categories--~~osa 'in the base-ne~t=al ex~act (Table IV) and
those in the acid extract (Table
v ).
Pesticides (Table III
that were" tentatively identified in the pesticide ~~alysis
.
will be confir.med by GC-~~.
The base-neutral extractablas may be separated and eluted
into the MS cnder the following chromatographic conditions:
Column - 6 foot, 2.0 mm inside diameter, glass
Packing - 1% SP2250 on 100/120 mesh Supelco~ort.
proqram - hold 4 ~~utes @ 500, program 500-2500
@ SO/min., hold 20 minutes @2600
Injector - 2750
Separator - 2750
Carrier gas - He @ 30 ml/min
Injection size - >2 ~l
-------
- 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 recommsnded 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 ~~ methods described below.
.
~t the beginning of each GC-MS run of a base-neu~ral
e~tract, the operator should demonstrate the ability to chro-
matoq:aph benzidine at the 40 ng level.
accomplished should the run be started.
Only after this is
If benzidine can be
.
c~~omatographed, the o~~er nitrogen-containing compounds of
Table IV can be chroma to graphed as well.
If desired, capillary or SCOT columns may be used instead
of the packed column of SP-22S0.
Coatings of OV-17 or SP-22S0
may be used.
The elution order of OV-17 and SP-22S0 are very
s~lar.
Some specific data for OV-17 is given L~ Table VII.
The performance criteria for benzidine must still be met
-------
- 2S -
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 - 1800 - 3000 @ SO/min
Injector - 2900
Separator - 2900
Carrier Gas - He @ 30 ml/min
Injection size - ~2 ~l
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 ~~e abil~ty to detect 100 ng of penta-
chlorophenol.
Mass Spectrometry should be conducted with a system
utilizing a jet separator for the GC effluent since mer.~rane
separators lose sensitivity for light molecules ~~d glass'
f:it separators inhibit ~~e elution of polynuclear aromatics.
A computer system should be interfaced to the mass spect=o-
meter to allow acquisition of continuous mass scans for ~~e
duration
of the chromatographic program.
The computer system
-------
- 26 -
should also be equipped with mass storage devices for
savi~g 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 t..~e presence of a compound by GC-MS, three
conditions must be met.
First, ~~e characteristic ions for
the compound (Tables III-V) must be found to maximize iri the
same spectr1Jm.
Second, the time at which the peak occurs
must be within a window of = 1 minute for the retention time
of this co~ound .
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 known that hexachlorobenzene elutes from the SP22S0
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 L~tensities of these ions
versus time (or ~1S scan number) anc the window from 18.4-20..4
minutes is examined for the simultaneous peaking of the in-
tensities of these ions.
If all three ions are present, ~~e
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.
-------
- 27 -
Tab1eIII1ists 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
exa~tly as the other base-neutral compounds.
The last four materials require special treat~ents.
Chlor-
dane is expected to produce ~~o main pe~~s within the retention
range given in which all three masses listed will maximize.
Toxaphene will produce several (5-15) pe~~s 'in which the masses
given will maximize within the retention time range.
For t..1.e
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 qeneral they will not maximize in
the same TIC ~eak.
For t..1.ese four materials in particular it
is necessary to also run a standard.
Because GC-MS is only
beinq used for con;irmation--and at its limit of detection--all
quantification w~ll be done by EC-GC for ~1.e pesticides.
The
methods for these four are not final ~~d feedback from the
field to Dr. Shackeiford is welcome.
~ihen a compound has been identified, the quantification
of that compound will be based on the integrated area from
the specific ion plot of ~~e first listed characteristic ion
in Tables rv, and
v.
Quantification will be done by the
internal standard method using deuterated anthracene.
Response
-------
- 28 -
factors, therefore, must be calculated to compare ~~e MS
response for known quantities of each priority pollutant with
that of the internal standard.
be calculated as:
The response ratio (R) may
R =- Ac x £!.
Aa Cc
. .
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 ~~thracene.
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 de~ection refer to the
values given in Tables III-V.
The concentration of a compound in the extract may now
be calculated using:
C =- Ac x Ca
Aa' 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 ~lot for deuterated an~~acene, and Ca is the concentration
...
of deuterated anth=acene 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 rv and
v
characteristic
CI ions for most compounds are given.
The use of chemical
ionization ~~ to support EI is encouraged but not required.
. .
5.
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 fro~
EMSL-Cincinnati, ~~ey are to be analyzed by solvent extraction
once each 20 working days and the results reported 'o'lith other
analytical data.
The 1% SP2250 and Tenax GC column packings are avaiiable
by request to EPA contractors from Dr. Walter Shackelford, EPA,
Athens, GA.
(1:)
Available f=6m PCR, 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 ~eater than the deuterated anthracene internal
standard, then it is not necessary to do a GC-MS analysis.
such peaks are seen, then the blank must be sent for full
If
priority pollutant analysis.
The contractor will look for all priority pollutants to
the limit of 10 ~g/l except in those cases listed in Tables IV-V
in which limits of detection are too high for analysis at this
level.
6..
Re~orting of ~
All concentrations should be reported in ranges--10 ppb,
100 ppb, and greater than laa 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 ~~e Athens Environmental Research Laboratorj 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 s~~ple r~~,
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 spect--um
END OF FILE
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, doc\JIt1entation and a table of MS res-
ponse ratios should be sent to:
Dr. W. M. Shackelford
Athens Environmental Research
College Station Road
Athens, GA 30601
Laboratory
-------
Table III.
":~3 -
pesticides
Compound Name
RRT1
,(hexach1orobenzene)
Detection Limit
(ng)
Characteristio
~I ions (ReI. Int.l
a-endosu1fan
a-DUC
y-DHC
a-nuc
aldrin
heptachlor
heptachlor epoxide
a-endosu1fan
dieldrin
4,41-00£
4,41-OOD
4,41-OOT
endrin
endosu~fan sulfate
0.51
1.02
1.09
1.12
1.14
1.15
1.23
. 1. 24
1.20
1.30
1.33
1.30
'1.41
1.41
40
40
40
40
40
40
4u
40
40
40
40
40
40
20
201(100), 283(40), 278(30)
103(lQO), 109(06), 181(91)
'1.31100),"109(96), 181(91)
101(100), 193(93), 109(62)
66(100), 220(11), 263(73)
100(100), 272(60), 274(46)
355(100), 353(79), 351(60)
201(!00), 283(40), 278(30)
79(100), 263(28), 279(22)
246(100), 249(64),176(65)
235(100), 237(76),165(93)
235(100), 237(72),165(59)
01(100), 82(6!), 263(70)
272(100), 397(75), 422(25)
6-DIIC
chlordane
toxaphene
PCB-1242
PCB-1254
1.14-1.37
1. 22-1. 47
0.93-1.24
1.18-1.41
183(100),109(86),
373(19), 375(17),
,(231, 233, 235) *
(224, 260, 294)*
(294, 330, 362)*
181(90)
377 (10) **
*
These ions are listed without relative intensities since the mixtures they rep~e~ent
defy characterization by three masses.
These three ions are characteristic for the a and y forms of chlordane. No stock
should be set in these three for other isomers.
'1>*
1
1\ SP-2250 08 100/120 mesh SupeAcoport in a 61 x 2 mm id glass column, Ue @ 30 m1/min;
Program: 50 for 4 min, then 9 /min to 2600 and hold for 15 min.
-------
''''4 -
Table IV.
Base-neutral Extractab1es
RRT 1 Limit of
(hexach10ro- Detectiof\ Characteristic CI ions
Compound Name benzeneL ~ EI ions (ReI. Int.) (Methane)
1,3-dichlorobenzene 0.35 40 146(100), 140(64)J 113(12) 146, 148, 150
1,4-dich1orobenzene 0.j6 40 146 (100),- 148 (64), 113 (11) 146, 148, 150
hexachloroethane 0.38 40 111(100), 199(61), 201(99) 199, 201, 203
1,2-dich1orobenzene 0.39 40 146(100),140(64), 113 (11). 146, 148, 150
bis(2-ch1oroisopropy1)
ether 0.41 40 45(100), 71 (19), 79 (12) 17, 135, 131
hexach1orobutadiene 0.55 .. 40 225(100, 223(63), 227(65) 223, 225, 227
1, 2, 4-trich1orobenzene 0.55 . 40 74(100),109(80),145(52) 181, 103, 209
naphthalene 0.57 40 128 (100), 127 (10), 129 (11) 129, 157, 169
bia(2-chloroethy1)ether 0.61 40 93(100), 63(99), 95(31) 63, 107, 109
hexach1orocyclopentadiene 0.64 40 237(100), 235(63), 272(~2) 235, 237, 239
nitrobenzene 0.64 40 77 (100), 123 (50), 65 (15) 124, 152, 164
bis(2-ch1oroethoxy)methane 0.68 40 93(100), 95(32), 123(21) 65, 107, 137
2-chloronaphtha1ene 0.76 40 162(100),164(32), 127(31) 163, 191, 203
acenaphthy1ene 0.83 40 152 (100), 153(16), 151(17) 152, 153, 181
acenaphthene 0.06 40 154(100), 153(95); 152(53) 154, 155, 183
isophorone 0.07 40 02(100), 95(14),138(18) 139, 167, 178
fluorene 0.91 40 166(100), 165(80), 167 (1.0 166, 167, 195
2,6-dinitroto1uene 0.93 40 165(100),63(72),121(23) 183, 211, 223
1,2-dipheny1hydrazine 0.96 40* 77 (100), 93(58), 105(28) 185, 213, 225
2,4-dinitrotoluene 0.98 40 165(100), 63(72), 121(23) 103, 211, 223
N-nitrosodipheny1amine 0.99 40* 169(100), 168(71),167(50) 169, 170, 198
hexach1orobenzene 1.00 40 284(100), 142 (30), 249 (24) 284, 286, 200
4-bromopheny1 phenyl ether 1.01 40 248(100), 250(99), 141(45) 249, 251, 277
phenanthrene 1.09 40 178(100), 179(16), 176(15) 178, 179, 207
anthracene 1.09 40 178(100), 179(16), 176(15) 170, 179, 207
dimethy1phtha1ate 1.10 40 163(100), 164(10), 194(11) 151, 163, 164
.diethy1phthalate 1.15 40 149(100), i78(25), 150 (10) 177, 223, 251
fluoranthene 1. 23 '40 202(100), 101 (23), 100(14) 203, 231, 243
pyrene 1. 30 40 202(100), 101(26), 100(17) 203, 231, 243
di-n-butylphth~late 1.31 40 149(100),:150(27), 104(10) 149, 205, 279
benzidine 1.38 40* 184(100).,92(24), 185(13) 185, 213, 225
butyl beozylphthalate 1. 46 40 149(100), 91)50) 149, 2'9, 327
-------
-'!18 -
Table IV.
nase-neutral Extractables (Cont'd.)
,
RRTl
(hexaohloro-
benzene)
Compound Name
1.46
1.50
1.54
1.66'
1.66
1.73
2.07
2.12
2.10
Limit of
Deteotion
(n9)
40
40
40
40
40
40
100
100
100
228 (100) ,
149(100),
2201100),
252(100),
252(100),
252(100),
276(101),
278(100),
276 (100),
Characteristio .
EX ions (Rel. Int.l
chrysene
bis(2-ethylhexyl)phthalate
benzo(a)anthracene
benzo(b)f1uoranthene
benzo(k)fluoranthene
benzo(a)pyrene
indeno(1,2,3-cd)pyrene
dibcn~o(a,h)anthraoene
benzo(~ h i)perylene
N-nitroso~imethylamine
N-nitrosodi-n-propylamine
4-chloro-phenyl phenyl ether
endrin ald~hyde
3,3'-dichlorobenzidine
2,3,7,O-tetrachlorodibenzo'-
p-dioxin
bis(chloromethyl)ether
deuterated anthracene (dlO)
229(19),
167(31),
229(19),
253(23) ,
253(23),
253(23),
130(28),
139(24),
130(37),
226(23)
279(26)
226(19)
125(15)
125 (16)
125(21)
277(27)
279(24)
277(25)
42(100), 74(88), 44(21)
130(22), 42(64), 101(12)
204 (100), 206 (34), 141 (29)
252(100), 254(66), 126(16)
322(100), 320(90), 59(95)
45(100),49(14),51(5)
180(100),94(19),00(18)
1.09
40
CI ions
JHethana l
228, 229, 257
149
228,
252,
252,
252,
276,
278,
276,
229, 257
253, 201
253, 291
253 i 201
277, 305
279, 307
277, 305
189, 217
1% SP-2250 0B 100/120 mesh supeAcoport in a061 x 2 rom id glass columnl He @ 30 ml/mini
Program: 50 for 4 min, then 8 /min to 260 and hold for 15 min.
Conditioning of column with base is required.
1
*
-------
... 3t,.
Table V.
Acid Extractab1es
RRTl Lim1 t of
Detection Chl'raoteristio CI 10ns
Compound Name (2-n1 tropheno1) (n9) E1 ions (ReI. Int.) . (Methane)
2-ch10ropheno1 0.63 .100 128 (100) , .6.4 (54), 130 (31) 129, 131, 157
. phenol 0.66 100 94(100), 65(17), 66(19) 95, 123, 135
2,4-dich10rophen01 0.96 100 162(100), 164(50), 98(61) 163, 165, 167
2-nitropheno1 1.00 100 139(100r, 65(35), 109(8) 140,160,122
p-ch10ro-m-cres01 1.05 100 142(100), 107(80), 144(32) 143, 171, 103
2,4,6~trich1orophen01 1.14 100 196(100), 190(92), 200(26) 197, 199, 201
2,4-dimethy1pheno1 1.32 100 122(100), 107(90), 121(55) 123, 151, 163
2,4-dinitrophen01 1.34 2 \JCJ 104 (100), 63 (59)., 154 (53) 185, 213, 225
4,6-dinitro-o-cres01 1.42 2 \Jg 198(100), 182(35), 77(28) 199, 227, 239
4-.n1 trophenol 1. 43 100 65(100), 139(45), 109(72) 140, 160, 122
pentachlorophenol 1.64 100 266 (100), 264(62), 268(63) 267, 265, 269
deuterated anthracene (dIO) 1.68 40 108(100), 94(19), 00(10) 109, 217
1
Column:
6' glass, 2 rom i.d.
Tengx GC - 60/og mesh
100 - 3000 @ 0 Imino
lie @ 30 m1/min
-------
- 37 -
'fable VI.
ELtJ'rION ORDER OF MOST OF THE S:E:].!IVOLATILE
PRIORITY POLLUT&~S ON 1% SP2250a
Co=ound
~,c
0.35d
0.35e
0.36d
0.38
0.39
0.47
0.51
0.52e
0.53e
o
0.53-
0.55
0.55
0.57
0.61
0.64
0.64
1,3-dichlorobenzene
2-chlorophenol
1,4-dichlorobenzene
hexaChloroethane
1,2-dichlorobenzene
bis(2-chloroisopropyl) ether
a-endosulfa:l
2,4-dimathyl phenol
2-ni-:roph.er..ol
2,4-dicnlorophenol
hexachlorobutadiene
1,2,4-trichlorobenzene
naphthalene
bis(2-chloroethy1)ether
hexachlorocyc1open~adiene
nitrobenzene
phenol
bis(2-chloroe~10r1)~~~ane
2,4,6-trichlorophenol
p-chloro-m-cresol
2-chloronaphthalene
acena~h t.."1y1ene
acenaphthene
isophorone
,fluorene
0.67
0.68
0.7le
0.73f
0.76
0.83
0~86
0.87
0.91
-------
- 38 -
Table VI. ELUTIOM ORDER OF MOST OF THE SEMJ:VOLATILE
PRIORITY POLLUTANTS ON 1% SP2250a (Continued)
a-endosul£an
dieldrin
4,41-DDE
~,c:
0.93
0.96
0.98
0.99
1.00
1.01
1.02
1.09~
1.09£
1.09
1.10
1.11£
1.12
1.14
1.15
1.15
1.23
1.23
1.24
I
1.28"
1.30
1.30
1.31
1.33
1.3Sd
.lJ:
1.41~
1.41
Compound
2,6-dinitratoluene
~,2-di?henylhydrazine
2,4-dinitroto1uene
N-nitrosodipheny1amine
he~achlorobenzene
4-bromopheny1 phenyl ether
a-BRC
y-BHC
phenanthrene
an t.."'lrac:~ne
dime thyl phthalate
penta~~oropheno1
a-BHC
aldrin
diethyl pht.~aJ.ate
heptachlor
heptachlor epoxide
fluoran thene
pyrena
di-n-buty1 phthalate
4,4'-DDD (p,p'-TDE)
4,4'--DD'r
endosu1£an sulfate
endrin
benzidine
butyl benzyl ph.thalate
c:h-rysene
-- L-3S--
1.46
1.46
-------
- 39 -
Table y~. ELUTION ORDER OF !-lOST OF THE SEMIVOLATILE
PRIORITY POLLU'I'F..NTS ON 1% SP2250a (Continued)
- . - - - h- - ~
Comcound
-
~,.c
1.50
1.54
1.66
1.66
1.73
2.07
2.12d
2.12f
bis(2-ethylhaxy1)phthalate
benzo(a)~~thracene
benz.o (b) fluoran1:hene
benzo(k)fluoranthene
benzo(a)pyrene
indeno(1,2,3-cd)pyrene
dibenzo(a,h) anthracene
benzo{ghilpery1ene
a 1% SP-2250 on 100/120 mesh supe1coport in a 6' x 2mm id
"glass column; He @ 30ml/min; Program: 50° for 4 min,
then aO/min to 260° and hold for 15 min.
b Relative to hexachlorobenzene at 19.4 min.
c 40nq. gives 5-90% response on FID unless otherwise noted.
d 200nq required to obtain 5-90% response on FID.
e 2 1J.g required.
f 40 ~q required.
-------
- 40 -
Table VI
(continued)
Standards not ava:il:a1:lle:
as of 2/8/77
N~nitrosodi-n-propyl~~e
4-~lorophenyl phenyl ether
TCDD
endrin aldehyde
N-nitrosodimethyl~~e
3,3'-dichlorobenzidine
bisCchloromethyl}ether (unstable/in water)
Standards1:hat wou1d not chromatograph:
4,6-dinitro-o-cresol
4-nitrophenol
2,4-dinitropheno1
Sta..~dards vie1dinq a ra.~qe of pea..tts:
RRl'b
0.93-1.24
1.18-1.41
1.22-1.47
1.14-1.37
PCB-1242
PCB-1254
toxaphene
chlordane
-------
- 41 -
Table VII.
Order of Elution tor
OV-17 SCOT Column
Compound
1,3-dichlorobenzene
1,4-dichlorobenzene
2-c:hlo:ophenol
1,2~dichlorobenzene
bis(2-C:hloroethyl}ether
phenol
bis(2~chloroisopropyl}ether
hexachloroethane
nitrobenzene
2-nia-ot:lhenol
1,2,4-trichlorobenzene
2,4-dimethylphenol
naphthalene
2,4-dichlorophenol
hexac:hlorobutadiene
isophorone
p-c:hloro-m-cresol
hexachlorocyclopentadiene
2,4,6-i:richlorophenol
ch1or~naph1:halene
2,4-dinitrotoluene
acenaphthylene
acenaphthene
dimethylph~~alate
fluorene
diethylphthala.te
N-nitrosodiphenylarnine
2,6-dinitrotoluen~
a-BHC
4-bromophenyl phenyl ether
~-BBC
hexachlorobenzene
a-SHC
phenanthrene
ant:.hracene
di -n-butylphthala te-
a.ldrin
flacranthene
pyrene
DDE
DDD
endrin
dieldrin
DCT ,
butyl benzyl phthalate
benzo(a)anthracene
chrysene
N . 2
St:lectrum umoer
-
134
137
141
153
163
165
173
178
194
219
234
240
240
244
262
272
317
325
332
339
312
374
390'
391
434
447
447
454
476
4i8
487
490
506
518
518
583
592
617
634
659
664
688
,688
713
713
748
748
-------
- 42 -
Table VII.
Continued
- --- -.----
Compound
bis(2-e~ylhexyl)ph~~alate
benzo(a)pyrene
benzo (b) fluo:anthene
benz~(k}fluoranthene
Spectrur- NUu~er2
804
906
970
970
1
33 meter qla~s OV-17 SC06 column,
Program: 60 ~ 2600 @ 6 /minute
2
Number of 2.5 second scans up to point of elution.
-------
- 43 -
Metals
1.
Sample Preparation
I
With the exception of mercury, the metals to be deter-
min~~ 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 ~~alyzed by flameless AA--Be, Cd, Cr, Cu, Ni,
Pb and Zn,
b)
those metals which are to be analyzed by flame less
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, s~~ples to
be ~~alyzed by flameless ~~ should be prepared as an industrial
effluent as described in "Atomic Absorption Newsletter;" 14,
page III (1975)
(Reference 8).
Note:
Nickel nitrate should
be added only to those aliquots on which the analysis of
selenium and arsenic are to be accomplished.
The sample
pr~p-
aration ~rocedure for antimony and beryllium analysis by flame-
-
less AA is the same procedure used for flame ~A.
The sample preparation procedure to be used for mercu:y
analysis is ~~at given in "Methods for Chemical ~~alysis
Water and Wastes (1974)", 8.1, page 124 (Reference 7).
of
-------
- 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.
Proced\U"e
a)
Flame AA - The procedures to be used are ~~ose
described in "Hethods for Chemical Analysis of
Water and ~astes (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.
-------
- 45 -
Table VIII
Element
Methods for Chemical
Analysis of Water and
Wastes, 1974*
Comments
Be
p. 99
Cd
p. 101
Analyze by flameless AA if
conc. <20 J1g/1
Analyze by flameless AA if
conc. <20 J1g/1
. .
Cr
p. 105
Use nitrous oxide-acetylene
flame for all analyses--analyze
by flameless AA if conc. <200 J1g/1
Cu p. 108 Analyze by flame1ess AA if
conc.
-------
1)
2)
- 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.
3)
A blank maximum temperature atomization, without
gas interrupt, should be accomplished before
4)
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
5)
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.
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 ~~e
volatilization temperature is known.
The ccm-
pound used should have a volatilization temper-
ature between 800 and l2000C.
7)
To insure that ~~ere is no loss from the acid
matrix prior to atomization, the optimum charring
temperature for eac~ metal should be established
in the same manner (i.e., by plotting charring
temperature versuS atomization signal of st~~dard
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 ~~e
nickel nitrate matrix) with an optimum charring temperature
of approximately l3000C.
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)
~~rcury analyses - The cold vapor technique as
described in "Methods for Ch~~cal Analysis of'Water
and Wastes, (1974)", page 118 (Reference 7) is to
be followed.
4.
Quality Assurance
a)
To verify that the instrument is operating correctly
within the expected performance limits, ~~ appropriate
standard should be included between every ten samples.
Spiked aliquots shall be analyzed with a frequency
b)
of 15% of the s~~ple load for each metal determined
by fl~e AA.
If the recovery is not within =10~ of
the expected value the sample should be analyzed by
method 0 f standard addi tion.
(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 fNhere t...i.e absorba..?lce in t...i.e
unspL~ed aliq-.lot was less than 0.1, and not more than
0.1 when t...i.e absorbance in t...i.e unspiked aliquot was
0.1 or greater.
-------
- 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)
~fuen 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 ~g/l, nearest ~gi 10 ~g/l and above, two significant figures.
-------
- 49 -
Cvanides
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.
Sample Procedure
2.
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.
Qualitv Assurance
3.
a)
Initially, demonstrate quantitative.re~overy 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 a=e to be established and confirmed as described
in Chapter 6 of the "Analytical Quality Control
Handbook" (Reference 9).
4.
Reporting of ~
Report cyanide concentrations as follows:
1.0 mq/l, nearest 0.01 mqi 1.0 mg/l and a:ove,
Less than
- . .~. ~
~wo s~gn~-~c~~~
figures.
-------
- 50 -
Phenols
Samole 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 SlOB for samples that contain less
than 1 mq/l of phenol.
Use method SlOe for samples that contain
more than 1 mq/l of phenol.
Qualitv Assurance
3.
Demonstrate quantitative recovery with each distillation
apparatus by comparing disti~led standards to non-distillea
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 ~ ~
Report phenol concentrations as follows:
Method SlOB to the nearest ug/l.
Method SlOe - when less ~~an 1.0 ug/l to the nearest
0.01 mqi 1.0 mq/l and above to two significent figures.
Report all ~ality control data when reporting results
of sample analysis.
-------
- 51 -
REFERENCES
1.
"Determining Volatile Org~~ics
"
by Gas Chromatography,
at Microgram-per-Liter Levels
T. A. Bellar and J. J. Lichter~erg,
2.
. Jour. AWWA, 6_6 , 739-744, Dec. 1974.
I':' .-
Reference Compound to Calibrate Ion Abundance Measurements
in Gas ChromatographY--Mass Spectrometry systems~ J. W.
Eichelberger, L. E. Ear=is and W. L. Budde, Anal. Chem. 11,
995-1000 (1975).
3.
ASTM A.."'Ulual Standards - Water, part 31, Metb.od D2908 "Sta."1dard
Recommended Practice for Measuring Water by Aqueous-Injection
.Gas Chromatog=aphy."
I 4.
ASTM Annual Standa=ds - Water, part 31, Method D3371 "'I'entati..;e
5 .
Meth~d of 'Test for Nitriles in Aqueous Solution by Gas Liquid
Chromatograph."
II , 1, ~. 11
D~rect Ana ys~s of ' Water S~~ples ~or 9rgan~c Po utants
. II
with Gas Chromatography-Mass Spectrometry,
Harris. L. E.,
Budde, W. L., and Ei~helberger, J. w.
Anal. Chem., ~,
1912 (1974).
6.
Federal Register, Volume 38, number 125, part II, Appendix !I,
r
p. 17319, Friday, Ju..-."e 29, 1975, "Determination o£ Organo-.
chlorine Pesticides in Industrial Effluents,"
7.
"
ItMethods for Chemical Analysis of Wa.ter a.."1d Wastes (1974) ~
u.s. Envi=onmantal Protection Agency, Tec~"101ogy T=a.~sfe=.
8.
IIDetermining Selenium in Water, Nastewater, Sedi:nent a..~d Sludge
II
by Flameless Atomic AbsOr?tion Spectroscopy, T. C. Martin and
'~~ t' '?e".s'~~.e~ '4 109 116 (1Q75)
J. F. Kopp, Ato~c ~SOrP ~on ~ ~ --~~ -'=-' - - -~ .
-------
,9.
10.
- 52 -
II. .
Handbook for Analytical Quality Control in Water and Waste-
"
water Laboratories (1972),
u.s. Environmental Protect~on
Agency, Technology Transfer.
"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-th~~-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 i~dustries-'
petroleum, t~~ery, 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 necessarj
because of intractable emulsions.
-------
- 54 -
APPENDIX I
(continued)
There is a justifiable concern that the ext~action 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) Analvsis
Although the 11 phenols of interest here do chromatograph on
the Tenax column cited, the chromatography is poor, particular~y
for ~~e 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 ~able IV.
.
It should be
noted, however, that 4-nitrophenol, 2,4-dinitrophenol, 4,G-dinitro-
o-cresol, and pentachlorophenol fail~d to give MS response at the
100 ng level using this column.
. SPIOae (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 a=e
eluted from SPIOee, but they produce broad peaks which are difficult
to quantify.
-------
- 55 -
Appendix II
Possible Sources for Some Priority Pollutant: Stand"ards
Compound.
acena"ph thene
acrolein
acrylonitrile
aldrin
dieldrin
benzene
benzidinel
carbon tetrachloride
chlordane (technical
Source of
Sta..~d.ard 2
(tetrachloromet:hane)
mixture & metabolites)
k't p. 118
AL p. 18
At. p. 19
HERr.. i80
HEro:. ~2380
B p. 154
RFR -
B .p~.-8.S.
HEro:. ~1200
Chlorinated benzenes (other than dichlorobenzenes)
chlorobenzene
1,2,4-trichlorobenzene"
hexachlorobenzene
AL p. 165
AL p. 710
At. p. 416
Chlorinated etha..~es (including 1,2-
dichloroethane, 1,1,l-trich1oroeth~~e
and hexachloroethane)
1,2-dichloro~thane
l,l,l-trichloroethane
hexachloroethane
l,l-dichloroethane .
1,l,2-trich1oroethane
1,1,2,2-tetrachloroethane
chloroethane
Chloroalky1 ethers Cchloromethyl, chloroethy1 and
mixed ethers)
At. p. 261
B p. 309
At, p. 416
PB p. 142
PE"? 388
PB p. 372
EA p. 53
bis{chloromethyl) eS~er1
bis(2-chloroethyl) ether
2-chloroethy1 vinyl ether
-- - p. .-------...
RFR
AL p. 173
AL p. 174
Chlorinated naphthalene
2-chloronaph~~alene
IaI p. 50
-------
- 56 -
Appendix II_-
possible Sources for Some Priority Pollut~~t Standards
(Continued)
Compound
Source of
Standard 2.
..
Chlorinated phenols (~ther than those listed
elsewhere;. includes trichlorophenc1s and
chlorinated cresols)
2,4,6-trichlorophenol
p-chloro-m-creso1
chloroform (trichloromethane)
2-ch1orcphenol
AI. p. 712
'rCI p. 102
B p. 92
AL p. 187
DOT and metabolites
4,4 . -DDT.
4,4'-DDE
4,4'-DDD (p,p'-TDE)
HER!. ~1920
HEP.L ~J:860
HERL f1780
Dichlorobenzenes (1,2-il,3-i and 1,4-
dichlorobenzenes)
1,2-dichlorobenzene
.l,3-dichlorobenzene
1,4~dichlorobenzene
AL p. 258
AL p. 258
AL p. 258
. Dichlorobenzidine
3i3'-dichlorobenzidinel
CPL p. 81
Dichloroethvlenes (1,1-dich1oroethy1ene ~~d
1,2-dichloroethy1ene) .
1,1-dichloroethylene
l,2-trans-dichloroethylene
2,4-dichlorophenol
AL. p. 746
AL p. 262
AI. p. 265
Dichlorcprop~~e and dichloropropene
1,2-dichloropropane
1,3-dichloropropy1ene (1,3-dichloropropene)
2,4-dLuethylphenol
AI. p. 267
AL p. 267
AI. p. 323
Dinitrotoluene
2,4-dinitrotoluene
2,6-dinitrotoluene
1,2-diphenylhyd=azine
PB p. 180
PB p. 180
AL p. 333
-------
- 57 -
Appendix .:rt
Possible Sources for Some Priority Pollutant Standards
(Continued)
Compound
-
Source of
Standard 2
Endosulfan and ~etabolites
a-en do suI fan
6-endosulfan
endosulfan sulfate
HEnL i3220
HERL i3200
NI p. 45
Endrin and metabolites
endrin
endrin aldehyde
HER!. i3260
NI p. 147
ethylbenzene
fluoranthene
B p. 161
;',N p. 1113
Haloethers (other than those listed 'elsewhere)
4-chlorophenyl phenyl ether (p-chloro-
diphenyl ether)
4-bromophenyl phenyl ether
bisC2-chloroisopropy1) ether
bis(2-chloroethoxy) methane
RFR p. 6*
ICN p. 37
PB
PB p. 62
Ha.lomethanes (other than those li::i"te'delse~.,here)
I!'.ethvlene chloride (dichloromethane)
methyl chloride. (chloromethane)
methyl bormide (bromomethane)
bromofo:tm (tribromomethane)
dichlorobromo~~thane
trichlorofluoromethane
dichlorodifluoromethane
chlorodib romome thane
PB p. 276
PB p. 277
PB p. 276
PB p. 73
CO p. 16
PB p. 358
PB p. 142
CO p. 27
Heptachlor and metabolites
heptachlor
heptachlor epoxide
hexachlorob~tadiene
HER!. i3860
HER!. ~3880
AL p. 416
Hexachlorobvclohexane (all isomers)
a-BHC
a-BHC
y-BHC
o-BHC
(lL-"dane)
HEm. ;'f620
HEro:. ~6 4 0
HEm. *680
HER!. ?o660
-------
- 5'8 -
Appendix II
Possible Sources fOr Some Priority Pollut~~t Standards
(Continued)
Compound
hexachlorocyclopentadiene
isophorone
naphthalene
n;i.trobenzene
Source of
Standard.2
AL p. 416
tAL p. 464
ANp. 1.18
AL p. 557
Nitrophenols (including 2,4-dinitrophenol and'
dinitrocresol)
2-nitrophenol
4-nitrophenol
2,4-dinitrophenol
4,6-dinitro-o-cresol
AL p. 564
AL p. 564
AL p. 332
TCI ~. 188
Nitrosamines
N-nitrosodime~~ylaminel
N-nitrosodi-n-propylamine
N-nitro sodiphenyl amine
pentachlorophenol
phenol
NI p. 173
FB p. 310
EA p. 159
AL p. 587
AL p. 595
Phthalate esters
. bis(2-ethylhexyl) phthalate
butyl benzyl phthalate
di-n-butyl phthalate
diethyl phthalate
dimethyl Fhthalate
POlychlorinated biphenYls (PCB's)
CS p. 8
CS p. 8
CS p. 8
CS p. 8
CS p. 8
PCB-1242 (Aroc lor 1242)
PCB-1254 (Aroc 10r 1254)
PQiynuclear aromatic hydrocarbons (including
benzanthracenes, benzopyrenes, benzo-
fluoranthene, chrysenes, dibenzan~~racenes,
and indenopyrenes)
HERL ~5703
HERL *5705
1,2-benzanthracene
benzo[a]pyrene (3,4-benzopyrene)
3,4-benzofluoran~~ene
11,12-benzofluoranthene
chrysene
&"1 p. 118
&"1 p. 118
NI
NI
&"1 p. 118
-------
- 59 -
Appendix I I
Possible Sources for Soms Priority Pollutant Standards
(Continued)
Compound
Source of
Sta.'Ildard 1
acenaphthylene
anthracene
1,12-benzoperylene
fluorene
phena."1 threne
1,2:S,6-dibenzanthracene
indeno (1,2,3-C,D)pyrene
pyrene
AN p. 1
Mt p. 118
AN p. 118
&~ p. 118
AU p. 118
AN p. '-118
AN p. 118
AN p. 118
2,3,7,8-tetrachlorodibenzo-p-dio:dn (TCDD)
tetrachloroethylene
toluene
toxaphene
trichloroethylene
vinyl chlQride (chloroethylene)
I-bromodecane (po~sible internal sta.~dard)
I-bromododeca.~e (possible internal standard)
NI p. 174
AI. p. 680
AI. p. 701
HEP..Li?6740
AI. p. 711
PB p. 406
Foot..'"lotes.:
1
These compounds or any mixture containing l~ 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 handlin~ are in the Federal
Register, Vol. 39, No. 20, pp. 3756-3797, 29 January 1974.
1
Only one source is listed even though several may be available
These sources are not to be interpreted as being endorsed bv
the EPA; they serJe to show at least one ven~cr where each -
standard can be obtained. When several sources Ttiere aT...a.ilable
and compound purity was listed, the source having the highest
purity material was selected.
These compo~'"lds have been ordered but have not been received
at Athens- ERL as yet.
*
------.- ---
-- .-"-------"- ..-
- - -e- -_e. --~-
-------
. AL
AN
B
CS
CPL
EA
ICN
NI
PB
RFR
HERL
co
TCI
- 60 -
Sources of Standards and p~b~eviations
Aldrich ~~emical Co., Milwaukee, Wise.; Catalog 1977-1978.
&~alabs, Inc., North Haven, Conn.; Catalog 18 (June 1976).
J. T. Baker Chemical Co., Phillipsburgh, N.J.;
Catalog 750 (July 1975). .
"Chem-Service, West Cheste~,
Pa. ;
Bulletin CS-100-8 (1975).
~~emical Procurement Laboratories, College Point, N.Y.;
1975 cataloc. .
-
Eas~~ Kod~~ Co., Rochester, N.Y.; Catalog 48
(1976) .
K&lC Rare & Fine Cb.emicals, P 1ai:1'..'ie~'; ,
(1975) .
N.Y.;
Catalog No. 10
~_._- ..
'95019
Nanogens International, P.O. Box 487, "E'J;:eeeom,...CA
"Na..'1ogen Inde:-::" (1975).
Pfaltz & Bauer Chemical Co., STamford, Conn.; Catalog
1976.
RFR Corp., Hope, R.I.; "Chemical Standards for Air-Water-
Industr.l-Foods" (1975).
"Analytical Reference Standards and Supplemental Data for
Pesticides ~~d Other Selected Organic Compounds", EPA-
660/9-76-012 (~sy 1976), Health Effects Research Laboratory,
Environmental Toxicology Division, Research Triang~e Park,
NC. A samDle order bl~~ for star-dards and the above
~ublication are attached.
...
Columbia Organics Catalog A-7, Co1~~ia, S.C.
( 19 75) .
Tridom Chemical Inc., Haut~auge, N.Y.,' Catalog No.1
(1976) .
-------
- 61 -
ENVIRON~~ TOXICOLOGY DIVISION
HEALTH ~FE:CTS RESE:A?.cH I.A30AA'I'O~
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Resea.:c:h Tria.."qle Park, Nor-..h Ca:olina .27711
SUBJECT: Inde.,,< of pestic:ides Analytic:a1 Refe:enc:e
Standards - Upda.te of Hailing List
DATE:
Jl:ne, 1976
FRO~I:
Health E:fects Resea:c:h r.a=o~to:y, ~,
Iteseuc:h 'r:"ia.ng1e Pa:k, l;C, U.S.A. 27711
AC3, Q: ") r'J1, l11-1 j)4~
(MD-o 9) (I . ..7. J' J - T/
List
TO:
All Laboratory Fac:ilities on our Zofa.ili..,g
~s copy of the 1976 :evision of" our ccstic:ides refe:enc:e standards
:index .was mailed t:o the add:ess ~p~earing qn 0:':: maili."c; list. As this
li~t is seve:a1 years old, we are su:e ~at a n~ber of a.ddr~s5es ~ve
~"ga.d ar.d that 50=e are probably no lonc;e: existent.
If you wish to ramain on ou:.:ail~g list to receive fut~e u?~ates
of ~~is p~lic:a.tion, would you be good enough to c:o=?lete the ~il-=ac:k
below, snip it off, and retu~ it to us. Co not taar off the ba.~~ cover
. --
t:o J:'at:u..-n to the add:ess sr.o...."'C..o ; If YOt.1 na,7e no use fo:: t..i.is p~lica.tio.,
b1.1t know of some ot.."ter individua.! within your o;rga.ni2:a.~ion who is con-
c:e:ned with pesticides a...,alY5is, ",'ould you convey this index, along: with
the C'.a.il::lack, to tha.t cerson.
-------------~
------------------------
'to:
. -. ~.
U. S. ~"viro~~ent:al Protection Aqen~!
H~a.l~~ E!~ects Researc:h La-~rato=y
Environmental Toxicology Division
Research 'triangle Park; NC, U.S.A. 27711 (}O-69)
~at.e
We wish to be retaL.-:ed on you: mailinq list: to
E:J of the Pesticides Sc~~da.rds I~de~. 'the add::ess
is ent;~cly correct and :e~uires no ch~~ges.
receive future updates
sho~~ on the L~velo~e
OWe have no inte:es: i.~ future updates o~ this public:...tio~.
cancel us from your mailL.,q list.
?lease
D We wish to be reta.i."ed on 'leur mailil'tq lis:, but the adc.ress shown
on t..'1e envelope should be cha:tged to read. (print or type)
Recipient
-------
- 62 -
R::Q.UEST f'OR A..'iALn'ICAL ~""EF~rc::z S~iCA?~S
Date
'rO:
Quality Assurance Section
Environ=ental 'roxicology Division,
EPA, KE:P.L, Research 'r:dan~le ic-k,
MD-69
NC 27711
Cate Re~est Rec~ / /
Shipme.~t Date / /
I,.U) Code No.
Order Filled :'\1'
CO NOT ~.zRIT.:: IN THIS S?AQ:
'!he fo1low~~ reference standa:ds a.:e r~ed for our proqram:
Catalo~ CcmpoUa'"\d Catalo~ COC1pou."'ld
Code (C&talQ~ Name) Code (Catalog N~e)
~':o. No.
I
I I
I
.
II
I
-
I
I
I
II f
. II I
If necess~], use back of sheet to com~lete
if this ~oGt is co==,lete
-------
:- 63 -
APPEN.DIX III
- CQ~LECTION- OF-.SANP.LEtioR SCREENING ANALYSES -.--.-- --..-
The initial characteriziltion (screening) of the vari'ed industrial
discharges covered by this program will be made on an analysis of
a composite effiuent sarnpl~. Any scheme for collecting a
c~mposite sample is, in effect a ~~thod for mechanically
integrating to obtain average characteristics or a discharge.
During the screanin; phase the sample composite can be used to
determine the average characteristics which would be
representative of that d1~charge. Simple composite samples are
those that arc ~~de up of a series of alfqucts of constant volume
col1ected at regular time intarvais in a single container. Some
situations may require flew or time p~cpcrtiona1 sa~!ing, this
determination will be ma.aa by ~,! individual project orficer
after considering his specific industrial category.
The determination or co:npcsiting period 2~, 48 or 72 hours ~,;.11 .
be made on a case by case b~sis. The duration of ccmpositing
will depend on the type or s~"ple being coilected, the type or
facility being sampled and the tims varying char~cteristics or
the discbarge. Tne rate or chang!! or fl O~I and other
characteri s ti cs of the di s charge and the accuracy ree:r..:i red \'11 11
also. influence the d\'!terminatior. of the corr.positir.g period. For
'example longer cOUipcsiting periods ~ould be warranted when les~
stable unit process operations are being sarnple~.
Collection £! S~~oles
1.
Collection or Comoosite Sa~~les for Liouid-Liouid Extraction
- - -
Collect a reQresentative composite sample. The'maximum time
interval betieen aliquot sampl~s shall be no longer than 30
mnnutes. Tne minimum aliquot size shall be lCa mi. The
sample must be collected with an ~utomatic sampler using the
equipment and me~'ods outlined be1c\'i. ~o\iniliitJrn compcsit;
volume must be 2 1/2 gallons.
Automatic Samole Collection
Sampler - A peristaltic purn~ automatic sampler wi~,
timer and a single glass ccrnpositing jug is required. The 2
1/2 - 3 gallon compositing bottle must be glass and cieaned
-------
- 64 -
as outlined belo\.t. New unused tubing must be used for the
sampling line and for the pump for each individual outfall or
samP1e location. Vacuum type autcmatic samplers ~ay be used
prov1ded 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
1.nsulated chest and ice. ~taintain the sample at 4.C during
the compositing procedure. At ~~e corepletion of the
compositing period seal the container wit~ a taflon lined
cap. Place the container in an insulated shipping container,
ice, and seat, then ship to the analytical laboratory.
Maintain at ~.C during transport and storage prior to
ana 1 ys is. ..
When sampling raw untreated industrial discharges which
are generally hi~h .n suspended so1ids it is imperative that
adequate sample flew rate be maintained throughout the sample
train in order ta effectively transport the so.l ~cs. .In.
horizontal runs, the velocity ~ust e~ceed the scour velocity.
while in vertical runs ~ie settling or the fall velocity must
be exceeded several ti~~s to assure adsquate transport of
soiids in the flow. rne equipment used in sampiing raw
discharges ~1en must have a minimum intake velocity of 2 feet
per second. rn the sampting of treated effluents just about
any cc~erica11y available auto~~tic liquid s~pter could ce
used.
When mora than one la~oratorv is invoived 1n the
analysis of the various para~eters, the s~~ple should if at
al' possible not be divided in the field but rather at the
contractors' iaboratorJ. For purpoSe of this progra~ the
composite wiil be divided into four parts. one part for
me tal s, ana lys i S J one for pes ti c:i des and pca IS, ene fer GC/~1S
compounds and one for the classic parameters.
.
Blend the cCu.posite sa~ple to provide a homogeneous
mixture including a representative suspension of any solids
i.n the contair.er. No specific method is required, har.d
stirring wi~, c1ean glass or tef10n rods. mechanical pacdies
or magnetic mixing with taflon coated stirring bars may be
used. r.tetal mixing devices may not be used.
Meta's - Withdraw a weil blended aliquot of the
composite sample. Using a glass funnel, rinse the sample
container with a small portion of the sample, then transfer
-------
- 65 -
250 - 500 mJ of sample to the bottle. 00 not add any
prese~ative to the samp.le just seal and prepare for-
ship~~nt. All s~ples 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 50 at
base of tag. Ship samples to the Chicago Regional Laboratory
at the addressed sh~#n.
u.s. Environmental Protection Agency
Region V, Centl'al Regional Laboratory
1819 W. Pershing Road
Chi cago t !11i no is' 50609
Ra'tl discharge or treat;c affluer.t
~~.~
Ng VaaZZOQ
~acion
s.mc:ler.
s.m=I. Poinc ..
-.
'. .~
Tv". s.n:::I,:'-G;3:1_C~~,ic'
. . -. .
CIU
,
\
:c .
- .
Ti",. :0"
Ptn_'Ci;es~:?' .
Plasma only
-------
- 6~ -
Field Blank Procedure for Automatic Samo1ers
8ian~ Water - Blank water must be as free from organic
interferences as possible. The analytical laboratory shculd
supply this water in bulk glass containers (minimum of five
liters) for field use. Tne supplying laboratory shall analyzs
the blank water.to determine the organic background that may be
present.
" Procedure - All parts of the s~piing system must be scrubbed
with hot detergent water and thoroughly rinsed with tap water and
blank water prior to use. Further rinsing with methylene
chloride is required ','rhen parts permit, i.e., are not susceptible
. to dissolution by the so1'ler.t. (riote: Tygon p1"astic tubing is a
source of phthalate ester contaminaticn. Where its use is
required, i.e., in the peristaltic PUhoP. the lensth must ce kept
as short as possib1e. Teflon is acceptable and may be used in
other parts of the sarn~ling system as in intake lines. In the
field, pump C10 1iters or blank water through the sampling line
and pump tubing and discard. Then pu~p three liters of blank
water through the system anc collect as a blank in a l-gal1on
sample bottle that has been prep~red as described below. Seal
the bottle with a Teflon iined cap. I"r.~diataiy ice t1! blank (4.
C) and ~ai"tain at (4.C) during the transport and storage prior
to analysis. .
Composi te Container - Prepare narrow-mouth g.1 ass s~pte
bottles for use by washing with hot detergent water ~nd
thorough ly. ri ns i"g wi:th tap "/a ter and blank \ia ter. Hea t the
bottles at 4CO.C in a muffle-rurnace or dry heat sterilizer for
30 minutes or alternatively. r.inse wi~, methylene chloride and
air dry at room tamperature protected frcm atcrnspheric or other
sources of contamination. Caps fer t1e bottles must be iined
wit, Teflon whi~, has been solvent rinsed as above.
2.
Collection £f. Grab Samoles
Collect grab samples ( minimum of one per day) for the
analysis of phenol, cyanide. and volatile organics
(purgable). Collect samples from the ra\'l process discharge.
the treated effluent, and ~~e treated effluent after
chlorination, when chlorination is practiced. It is
recommended that t,e samples be collected frem mid~ch~r.nel
at mid-depth. . S~ples should be collected ,~t a turbulent.
we1l mixed section of the channel.
-------
- 67 -
Cyanfde (Total)
Container - Use new one-liter plastic bottles that wilT
not contaminate the sample. Wash the bottles and caos with
hot water and thoroughly rinse with tap water and blank
water.
Collect a 1-1iter samele.
. .
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
(KI-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 0.6 9 of ascorbic acid ror
each liter of sample volume. Then add 2 ml or 10 N sodium
hydroxide per liter o~ sample (pH ~ 12).
Sea' the sample bottle and place in an insulated chest
and ice (4.C). Seal the chest and ship to the analyticai
laboratory. Maintain at 4.C during transport and storage
keep out of direct light prior to analysis.
Phenols
Container - Use new one-liter glass bottles. Wash the bottle
and Teflen cap liner with hot water and thoroughly rinse with tap
water and blank water.
, Collect a l-liter sample.
Preservation'. At ~ie ~i~e of collection, acidify the sample
by addition of phospheric acid or sulfuric to pH ~. .Note ~oluwe
of acid added on s~i.ple tag. Seal bottle, place In lr.su1a~d
chest and ice (4.C). Sea1 chest and "ship to analytical
taboratory. Maintain at 4.C during. transport and storage. Keep
out of direct light prior to analysls.
-------
- 68" -
Organics (Purge and. Trap Method)
Centai ners - Use 45 to 125 ml s.cre\'~ cap gl ass vi a 1 s wi th
Teflon faced. sileone septa:
Yials(a)- Pierc~ ~13074 or equivalent
S~Pta(a)~ P,erce 112722 or equivalent
Wash the bottles, septa, and caps with hot water and
thoroughly rinse with tac water and blank water. Heat the
bottles and septa at lOS-C fer one hour, co01 to room temperature
in an enclosed contaminant free area. When cool, seal bottles
'liith septa (Tefl en side dc~,") and scre\'t cae. ~!aintain the
bottles in .this conditicli until just prior' to fining' with blank
water or sampie.
(a) Available from Pierce, Iroc. Box 117, Rockford, !L 61105.
Collect duplicates 45-125 rnt samples each time sampies are
collected. Two bialiK water samples, sealed in 45 ml vials, are
to accompany the !~~ple bottles ~uring snip~ent to and from the
.sampling site. If preservation for residual chlorine is to ce
used, collect four samples during each sampiing period. Two
should be preserved and tdO not preserved. ' Two preserved and tdO
non-preservad blanks are to be provided.
Filling and Sealing cottles - Slowly fill each containar to
overncn.ting. Careful1y set the conta.iner on a lel/el surface.
Place the septum (Tef1on side dewn) on the convex s~ple
meniscus. Seal the s~iple with the scr;w cap. To insure that
the sample has oeen properly sealed, ir.vert the sample and
lightly tap the tid on a solid surface. ine absence of entrapped
air bubbles indicates a proper seal. If air bubbies are preser.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
chTorine. .ihe production or ~~lorcf~rm and other halcforms
continues in such samples if they are not stabilized. Waste
streail~ that have been treated with ~~lorine should be tested on
-------
- 69 -
site to determine whether or not preservative ;s needed. !f
preservatation is required, collect coth preserved and non-
preserved samples. Wrap the samples with wat~r 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.
Identi fi ca ti on ~ Same 1 as
All s&T.ples and blanks must be carefully identified
using water proof labels ar.d water proof ink. Include the
fanowing inTorr:taticn on the label: Sar.ipia numoer, cate and
hour of sampl1r.g, complete fnfo~~tion as to source anc
sampling'point, preservative acded, if any, and name of
persen collecting the s~ple (include addres3 God/or phone
ntm'JJer) .
------- |