PROCEDURES FOR ANALYSIS OF
PULP, PAPER, AND PAPERBOARD EFFLUENTS
FOR
TOXIC AND NONCONVENTIONAL POLLUTANTS
EFFLUENT GUIDELINES DIVISION
OFFICE OF WATER AND WASTE MANAGEMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20430
DECEMBER 1980
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PROCEDURES FOR ANALYSIS OF
PULP, PAPER, AND PAPERBOARD EFFLUENTS
FOR
TOXIC AND NONCONVENTIONAL POLLUTANTS
EFFLUENT GUIDELINES DIVISION
OFFICE OF WATER AND WASTE MANAGEMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
DECEMBER 1980
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LIST OF ABBREVIATIONS
ACS American Chemical Society
AID Analog/digital signal conversion
amu atomic mas unit
Celsius
cm centimeter
DFTPP Deca fluorotriphenyl phosphine
g gram
GC gas chromatograph
GC/MS gas chromatography/mass spectrometry
HP Hewlett Packard
ID inside diameter
1 liter
lb pound
m/e mass to charge ratio
mg milligram
ml milliliter
mm millimeter
mm minute
MS mass spectrometer
MSTFA N-inethyl-N-trimethyls ilyltrifluoroacetamide
N normal
Neff effective theoretical plates
ng nanogram
OD outside diameter
PFBB pentafluo rob romobenzene
PPTBA perfluorotributylammne
ppb parts per billion
ppm parts per million
RR response ratio
RT retention time
sec second
TFE teflon
p micro
v/v volume/volume
less than
> greater than
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ABSTRACT
A program was undertaken to verify the presence of those of the 129 toxic
pollutants and 14 industry specific nonconventional pollutants found during
the screening phase and to obtain information on the quantity of toxic and
nonconventional pollutants present in pulp, paper, and paperboard industry
wastewaters. Eighteen volatile organics and 33 extractable organics (in-
cluding 13 nonconventional pollutants specific to the pulp, paper, and paper-
board industry) were investigated in the verification program.
The procedures used to analyze samples collected during the verification
program are the same as method 624 and 625 proposed under authority of sec-
tions 304(h) and 501(a) of the Act (see 40 CFR Part 136: 44 FR 69464 [ Decem-
ber 3, 1979]), and provide for substantial quality control/quality assurance
(QC/QA) using surrogate standards, field blanks, method blanks, and replicate
analysis.
Surrogate standards were used extensively to monitor the integrity of all
analyses. Experimental methods were developed which facilitated gas chromato-
graphy/mass spectrometry (GC/MS) quantification of widely diverse extractable
organic compounds in a single analysis. Derivatization procedures were evalu-
ated to enhance the chromatography of phenolic and acidic compounds. Low
resolution reference mass spectra of TMS derivatives were established for
identification purposes. Retention times, characteristic ions, and other
GC/NS parameters are given which define the analytical methodology.
1].
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This document presents the detailed analytical procedures used in the verifi-
cation of pulp, paper, and paperboard industry wastewaters for toxic and
nonconventional pollutants.
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TABLE OF CONTENTS
Section Title Page No.
LIST OF ABBREVIATIONS i
ABSTRACT ii,iii
TABLE OF CONTENTS iv
LIST OF TABLES v
I. INTRODUCTION 1
II. ANALYSIS OF VOLATILE ORGANIC POLLUTANTS . 6
o Scope and Application 6
o Summary of Method 6
o Interferences 9
o Apparatus and Materials 10
o Reagents 11
o Calibration 14
o Quality Control 16
o Sample Collection, Preservation,
and Handling 18
o Sample Extraction and GC/NS Analysis 18
o Identification and Quantification 20
III. ANALYSIS OF SENIVOLATILE ORGANIC POLLUTANTS 23
o Scope and Application 23
o Summary of Method 23
o Interferences 26
o Apparatus and Materials 27
o Reagents 28
o Calibration 31
o Quality Control 33
o Sample Collection, Preservation,
and Handling 35
o Sample Extraction 36
o Derivatization 38
o GC/MS Analysis Techniques 38
o Identification and Quantification 38
o Recovery of Surrogate Standards 40
REFERENCES 42
BIBLIOGRAPHY 43
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LIST OF TABLES
Table No. Title Page No.
1 TOXIC AND NONCONVENTIONAL POLLIJTANTS UNDER
INVESTIGATION IN VERIFICATION SAMPLING PRO-
GRAM FOR THE PULP, PAPER, AND PAPERBOARD
INDUSTRY 4
2 TOXIC AND NONCONVENTIONAL POLLUTANTS APPLI-
CABLE FOR GC/MS VOLATILE ORGANIC ANALYSIS 7
3 TYPICAL DETECTION LIMITS FOR VOLATILE OR-
GANIC POLLUTANTS 8
4 GC/MS VOLATILE ORGANIC ANALYSIS PARAMETERS 15
5 SURROGATE STANDARDS FOR VOLATILE ORGANIC
ANALYSIS 17
6 GC/MS CHARACTERISTICS OF VOLATILE ORGANIC
POLLUTANTS 21
7 TOXIC AND NONCONVENTIONAL POLLUTANTS APPLI-
CABLE FOR GC/NS SENIVOLATILE ORGANIC ANAL-
YSIS 24
8 TYPICAL DETECTION LIMITS FOR SEMIVOLATILE
ORGANIC POLLUTANTS 25
9 GC/MS SENIVOLATILE ORGANIC ANALYSIS PARA-
METERS 32
10 SENIVOLATILE ORGANIC ANALYSIS SURROGATE
STANDARDS 34
11 GC/MS CHARACTERISTICS OF SENIVOLATILE
ACID - NEUTRAL EXTRACTABLE POLLUTANTS 39
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SECTION I
INTRODUCTION
In 1976, EPA was sued by several environmental groups and, in settlement of
this lawsuit, EPA and the plaintiffs executed a “Settlement Agreement” which
was approved by the court. This Agreement required EPA to develop a program
and adhere to a schedule for promulgating, for 21 major industries, BAT efflu-
ent limitations guidelines, pretreatment standards, and new source performance
standards for 65 “priority” pollutants and classes of pollutants. (See
Natural Resources Defense Council, Inc . v. Train , 8 ERC 2120 [ D.D.C. 1976],
modified 12 ERC 1833 [ D.D.C. 19791).
On December 27, 1977, the President signed into law the Clean Water Act of
1977 (PL 95-217). Although this law makes several important changes in the
Federal Water Pollution Control Program, its most significant feature is its
incorporation into the Act of many of the basic elements of the Settlement
Agreement for toxic pollution control.
As a result of the Clean Water Act of 1977, all pollutants are classified in
one of three categories:
1. conventional pollutants
2. toxic pollutants
3. nonconventional pollutants
Included in the conventional pollutant category are 5-day biochemical oxygen
demand (BOD5), total suspended solids (TSS), p1!, oil and grease, and fecal
coliform.
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The toxic pollutants consist of 65 classes of pollutants as represented by the
129 specific pollutants listed in the Settlement Agreement between EPA and the
Natural Resources Defense Council, Inc. (NRDC).
Nonconventioaal pollutants are those not included in one of the previous cate-
gories of pollutants. Discharge of pollutants may be industry-specific and,
if warranted, may be regulated. In addition to industry-specific compounds,
chemical oxygen demand (COD), ammonia, and color are also nonconventional
pollutants.
As a result of project investigations undertaken by the Agency in fulfillment
of the requirements of the Settlement Agreement and the Clean Water Act, 14
noncoriventional pollutants specific to the pulp, paper, and paperboard indus-
try were identified. These pollutants were added to the list of compounds for
which analyses were conducted during the screening program. Table 1 includes
the 14 noncoaventional pollutants specific to the pulp, paper, and paperboard
industry.
A screening program was established to determine the presence or absence of
the 129 toxic and 14 additional nonconventional pollutants. The procedures
used to analyze wastewater samples during screening, Sampling and Analysis
Procedures for Screening of Industrial Effluents for Priority Pollutants (EPA,
Cincinnati, Ohio, April 1977) and Procedures for Screening of Pulp, Paper , and
Paperboard Effluents for Fourteen Nonconventional Pollutants (EPA, Washington,
D.C., December 1980), also allow for calculation of the approximate quantity
of specific toxic pollutants and the additional 14 nonconventional pollutants.
This information was used to develop a verification sampling program.
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A verification program was undertaken to verify the presence of the compounds
found during the screening program and to obtain information on the quantity
of toxic and nonconventional pollutants present in pulp, paper, and paperboard
industry wastewaters. Additionally, several compounds whose usage was repor-
ted by industry were included on the list of verification parameters. The
organic compounds under investigation are contained in Table 1.
The samples from each verification mill were analyzed for 18 volatile organics
and 33 semivolatile organics. Included in the semivolatile organics were 13
resin and fatty acids and bleach plant derivatives, nonconventional pollutants
specific to the pulp, paper, and paperboard industry.
The procedures used to analyze samples collected during verification sampling
are the same as Methods 624 and 625 proposed under authority of sections
304(h) and 501(a) of the Act (see 40 CFR Part 136: 44 FR 69464 [ December 3,
1979]) and provide for additional quality control and quality assurance over
those procedures used during the screening phase.
The verification program included the implementation of a quality control!
quality assurance (QC/QA) program consisting of surrogate standards, field
blanks, method blanks, and replicate analysis. Surrogate standards were
selected to provide QC/QA data on primary groups of pollutants under evalua-
tion in the verificatjon program.
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TABLE 1. TOXIC AND NONCONVENTIONAL POLLUTANTS UNDER
INVESTIGATION IN VERIFICATION SAMPLING PROGRAM FOR TIlE
PULP, PAPER, AND PAPERBOARD INDUSTRY
Toxic Pollutants
benzene di-n-octyl phthalate
chlorobenzene diethyl phthalate
1 ,2-dichloroethane chrysene
1,1, 1-trichioroethane anthracene
1, 1-dichioroethane phenanthrene
1,1,2, 2-tetrachloroethane tetrachloroethylene
trichlorophenol* toluene
chloroform trichioroethylene
2, 4-dichiorophenol bromoform
ethylbenzene pentachiorophenol
fluoranthene carbon tetrachloride
methylene chloride 2 - chiorophenol
dichiorobromomethane 2, 4-dinitrophenol
trichiorofluoromethane butyl beazi phthalate
chlorodibromomethane para-chioro—meta—cresol
isophorone acenaphthylene
naphthalene pyrene
phenol
bis (2-ethyihexyl) phthalate
di-n-butyl phthalate
Nonconventional Pollutants
oleic acid 3,4,5—trichloroguaiacol
linoleic acid tetrachloroguaiacol
linolenic acid monochlorodehydroabietic acid
pimaric acid dichiorodehydroabietic acid
isopimaric acid 9,10-epoxystearic acid
dehydroabietic acid 9,1O-dichlorostearic acid
abietic acid xylenes
*Includes 2,4,5-trichlorophenol and 2,4,6-trichiorophenol
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These compounds were selected because of their similarity to the compounds
under investigation. By adding surrogate standards to each sample analyzed by
GC/NS, it was possible to assess system performance on a per-sample basis.
Recovery of the surrogate standards in the volatile organic analysis assured
that the apparatus was leakproof and that the analysis was valid. For ex-
tractable organic analyses, percent recoveries of the surrogate standards
indicated the complexity of the sample matrix and the validity of the analy-
sis. In each case, low recovery of surrogate standards signaled possible
instrument malfunction or operator error. For analysis of volatile organic
compounds, the area of the 100 percent characteristic ion for each surrogate
standard had to agree within 25 percent with the integrated peak area obtained
from analysis of the composite standard or the GC/NS sample run was repeated.
Semivolatile organic analysis was repeated if surrogate standard recoveries
were less than 20 percent.
The procedures used in the verification sampling program are detailed in this
document.
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SECTION II
ANALYSIS OF VOLATILE ORGANIC POLLUTANTS PRESENT IN
PULP, PAPER, AND PAPERBOARD INDUSTRY WAS TEWATERS
1. Scope and Application
1.1 This method is suitable for the determination of 18 volatile organic
toxic and nonconventional pollutants listed in Table 2.
1.2 This method is applicable to the determination of these compounds in
pulp, paper, and paperboard industry wastewaters.
1.3 The sensitivity of this method is usually dependent on the level of
interferences rather than instrumental limitations. The limits of
detection listed in Table 3 represent sensitivities that can be
achieved in wastewaters under optimum operating conditions.
1.4 This method is recommended for use only by experienced GC/MS anal-
ysts or under the close supervision of qualified persons.
2. Summary of Method
2.1 An inert gas is bubbled through a 5 ml water sample contained in an
appropriately designed purging chamber. The volatile organic com-
pounds are transferred from the aqueous phase to the gaseous phase.
The gas is swept through a short sorbent tube where the volatile
toxic pollutants are trapped. After the purge is completed, the
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TABLE 2. TOXIC AND NONCONVENTIONAL POLLUTANTS APPLICABLE FOR
GC/11S VOLATILE ORGANIC ANALYSIS
benzene 1, 2-dichioroethane
bromoform ethylbenzene
carbon tetrachioride methylene chloride
ch lorobenzene 1,1,2, 2-tetrachioroethane
chiorodibromomethane toluene
chloroform tetrachioroethylene
dichiorobromomethane 1,1, 1-trichioroethane
1, 1-dichioroethane trichioroethylene
trichlorofluo romethane
xyl ene s
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TABLE 3. TYPICAL DETECTION LflrIITS FOR VOLATILE ORGANIC POLLUTANTS
Concentration
Compound ( .ig/1)
benzene 1
bromoform 1
carbon tetrachioride 1
ch lorobenzene 1
ch lorodibromomethane 1
chloroform 1
dichlorobromomethane 1
1, 1-dichioroethane 1
1, 2-dichioroethane 1
ethy lbenzene 1
methylene chloride 1
1,1,2, 2-tetrachioroethane 1
tetrach loroethylene 1
toluene 1
1,1, 1—trichioroethane 1
trichloroethylene 1
trichiorofluorornethane 3
xy lenes 1
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trap is heated and backflushed with gas to desorb the compounds into
a GC/NS system. A temperature program is used in the GC system to
separate the components before entrance into the mass spectrometer.
2.2 If interferences are encountered, the given parameters can be varied
to optimize resolution of determinate compounds from interferences.
3. Interferences
3.1 The analytical system must be demonstrated to be free from inter-
ferences under the conditions of the analysis by running method
blanks. Nethod blanks are run by charging the purging device with
organic-free water and analyzing it in a normal manner. The use of
rubber components in the purging device should be avoided (i.e.,
non-TIE plastic tubing, non—TIE thread sealants, or flow control—
lers).
3.2 Samples can be contaminated by diffusion of volatile organics (par-
ticularly methylene chloride) through the septum seal into the
sample during shipment and storage. A sample blank prepared from
organic-free water and carried through the sampling and handling
procedures can serve as a check on such contamination.
3.3 Cross contamination can occur whenever high level and low level
samples are sequentially analyzed. To reduce the likelihood of
this, the purging device and sample syringe should be rinsed out
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twice between samples with organic-free water. Whenever an unusual-
ly concentrated sample is encountered, it should be followed by an
analysis of organic-free water to check for cross contamination.
4. Apparatus and Materials
4.1 Sampling equipment for discrete sampling.
4.1.1 Vial, with crimp caps-—l25 ml capacity. Wash the vial
with detergents, rinse it with detergents, rinse it with
water and then dry it at 105°C for one hour before use.
4.1.2 Septa——Teflon—lined silicone. Rinse the septa with or-
ganic free water and dry it at 105°C before use.
4.2 Purge and trap device whose equipment consists of three separate
pieces of apparatus:
4.2.1 The purging device is constructed from glass tubing with a
glass frit installed at the base of the sample reservoir.
Finely divided gas bubbles pass through the frit into the
aqueous sample.
4.2.2 The trap is a short section of stainless steel tubing
packed with an adsorptive material which retards the flow
of volatile compounds while allowing the purge gas to
vent.
4.2.3 The desorber is an auxiliary carrier flow system which
transfers the adsorbed compounds from the trap at elevated
temperatures onto the gas chromatographic column.
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The complete device can be constructed in the laboratory according
to the specifications of Bellar and Lichtenberg (1), or purchased
commercially.
4.3 Gas chromatograph/mass spectrometer system--complete with program-
mable gas chromatograph and all required accessories including:
column supplies, recorder, gases, and syringes. A computerized data
system capable of storing continuous mass spectral data and inte-
grating extracted ion profiles is required(Hewiett Packard 5980
GC/MS and SI-150 data system or equivalent).
4.4 Micro syringes——i, 10, 25, 100, 250 p1.
4.5 Vial--i ml crimp top with Teflon cap liner.
4.6 GC colunin--0.l% SP 1000 on 80/100 Mesh Carbopack C.
4.7 Magnetic stirrer.
5. Reagents
5.1 Sodium thiosulfate (ACS) granular.
5.2 Trap materials.
5.2.1 Porous polymer packing 60/80 mesh chromatographic grade
Tenax GC (2,6-diphenylene oxide).
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5.2.2 Stainless steel tube——19.1 cm (7.5 inches) long x 0.64 cm
(1/4 inch) OD.
5.3 Organic-free water.
5.3.1 Organic-free water is defined as water free of interference
when employed in the purge and trap procedure described
herein. It is generated by passing tap water through a
carbon filter bed containing about 1 lb of activated carbon.
5.3.2 A water system (Millipore Super-Q or equivalent) may be used
to generate organic-free deionized water.
5.3.3 Organic-free water may also be prepared by boiling water for
15 minutes in the following maimer: Maintaining the temper-
ature at 90°C, bubble a contaminant-free inert gas through
the water for one hour. While still hot, transfer the water
to a narrow mouth screw cap bottle with a Teflon seal.
5.4 Stock standard solutions are prepared in organic-free water. Be-
cause of the toxicity of some of the compounds, primary dilutions of
these materials should be prepared in a hood.
5.4.1 Fill a 1000 ml volumetric flask with organic-free water.
Cool the flask and water in an ice bath while constantly
stirring it with a magnetic stirrer.
5.4.2 Add the assayed materials.
5.4.2.1 Using a 1 jil syringe, inject each compound of
interest below the surface of the water quickly.
5.4.2.2 Keep the standard cold and the flask stoppered
when compounds are not being added. To thoroughly
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mix the stock standard, stir the solution for
approximately one hour after the final addition.
5.4.3 Calculate the concentration of the stock standard from the
density data for each compound.
5.4.4 Use a pipette to transfer the standard into 1 ml vials.
Make certain that there are no air bubbles in the vials
before sealing with Teflon-lined tops.
5.4.5 Store stock standards at 4°C. All standards must be re-
placed with fresh standard each month.
5.5 Surrogate standard solutions are prepared in organic—free water.
Primary dilutions of these materials should be prepared in a hood.
5.5.1 Fill a 100 ml volumetric flask with organic-free water.
Cool the flask and water in ice and stir.
5.5.2 Add the surrogate compounds:
5.5.2.1 Using a 10 p1 syringe inject each compound below
the surface of the water quickly.
5.5.2.2 Keep standard cold and the flask stoppered. Allow
the solution to mix thoroughly before storing in
vials with Teflon-lined seals at 4°C.
5.6 Antifoam solution--3 percent Antifoam C in deionized water. Dilute
stock 30 percent emulsion (Sigma Chemicals, St. Louis, Missouri,
63178) 1:10 v/v with organic—free water.
5.7 Perfluorotributylamine (PFTBA)--tuning compound (PCR, Inc., Gaines-
ville, Florida).
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5.8 Pentafluorobromobenzene (PFBB)--tuning compound (PCR, Inc., Gaines-
ville, Florida)
6. Calibration
6.1 Tune the mass spectrometer according to the manufacturer’s specifica-
tions with PFTBA. Verify the spectrum of PFBB according to publish-
ed guidelines. Analytical GC/MS parameters are given in Table 4.
6.2 Inject 250 il of a stock standard containing all compounds assayed
(compounds of interest and surrogate standards) into 5 ml of organic-
free water previously transferred to the sparging device (bubbler).
Inject 2 Ml of 3 percent antifoam solution (5.6) into the sparging
device.
6.3 Analyze this aqueous solution according to the purge and trap pro-
cedure (Section 9).
6.4 After the GC/NS run is complete, integrate the areas of the charac-
teristic ions of each compound in the standard. These data supply
reference retention times and mass spectra necessary for identif i-
cation and quantification of each compound in the samples. Adjust
GC/MS response to obtain an integrated peak area at m/e 100 of
75-100,000 counts/200 ug of l,l,l-trichloroethane in the composite
standard.
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TABLE 4. GC/MS VOLATILE ORGANIC ANALYSIS PARMIETERS
Sparging Conditions
Sample size: 5.0 ml + surrogate standard spike
Sparge volume: 450 ml (30 mi/mm x 15 mm)
Sparge gas: UHP nitrogen
Absorbent medium: 60/80 mesh Tenax GC
Trap dimensions: 19.1 cm (7.5 inches) long x 0.64 cm (1/4 inch) OD
stainless steel
Desorption Conditions - Backflushing
At 200°C with 20 mi/mm helium backflush for 8 mm, GC oven at -30°C
Mass Spectrometer - HP 5980/SI-150 Data System
amu Range: 20-300
Integration time: 6 millisecond/amu
Source temperature: 150°C
Silicon membrane separator
Gas Chromatograph
Start GC/MS scanning at -30°C
Reset oven to 50°C. Temperature program of 50°C to 220°C at
8°C/mm; hold at 220°C for 16 mm
Helium flow carrier: 20 ml/min
Column: 0.1% SP 1000 on 80/100 Mesh Carbopack C
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7. Quality Control
7.1 Before processing any samples, the analyst should demonstrate daily
through the analysis of an organic-free water method blank contain-
ing antifoam solution that the entire analytical system is inter-
ference—free.
7.2 Standard quality assurance practices should be used with this meth-
od. Field blanks should be collected to validate the sampling,
storage, and analysis process. Laboratory blanks should be analyzed
to validate the integrity of the analysis. Samples should be spiked
with surrogate standards to validate the accuracy of the analysis.
After each GC/MS analysis, profile the extracted ion currents of the
characteristic ions of the surrogate standards and integrate the
peak areas. The areas of the characteristic ions for each surrogate
standard must agree within 25% with the integrated peak areas ob-
tained in a daily composite standard analysis (6.2). Table 5 lists
the surrogate standards.
7.3 The analyst should maintain constant surveillance of both the per-
formance of the analytical system and the effectiveness of the
method in dealing with each sample matrix by spiking each sample,
standard, and blank with 5.0 p1 of surrogate standard solution
(5.5). Recovery of the surrogate standards assures that the purge
and trap apparatus is leakproof and that each GC/?IS analysis is
valid. Prepare fresh surrogate standard solution monthly.
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TABLE 5. SURROGATE STANDARDS FOR VOLATILE ORGANIC ANALYSIS
methylene chloride-d 2
1 ,2-dichloroethane—d 4
1,1, 1-trichloroethane-d 3
benzene-d 3
toluene-d
2—xylene-
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7.4 Linearity of the entire system should be checked monthly over the
range of concentrations commonly encountered in sample analyses.
The composite standard (6.2) in various dilutions can be used for
GC/MS linearity checks.
8. Sample Collection, Preservation, and Handling
8.1 Grab samples must be collected in glass containers having a total
volume in excess of 40 ml. The sample bottles must be filled so
that no air bubbles pass through the sample as the bottle is being
filled. Seal the bottles so that no air bubbles are trapped in it.
The sample should remain hermetically sealed until the time of
analysis.
8.2 The samples must be iced or refrigerated from the time of collection
until extraction. If the sample contains residual chlorine, add
sodium thiosulfate as a preservative (10 mg/40 ml will suffice for
up to 5 ppm of chlorine) to sample bottles at the sampling site.
Fill with sample just to overflowing, seal the bottle, and shake
vigorously for one minute.
8.3 All samples must be analyzed within 14 days of collection.
9. Sample Extraction and GC/MS Analysis
9.1 Purge a clean, empty bubbler for 15 minutes with ultra-high purity
(1JHP) nitrogen while applying heat (heat gun) to cotinectors.
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9.2 Cool. a previously heated (approximately 200°C) Tenax trap to room
temperature and attach to the bubbler. Transfer exactly 5 ml of the
sample to the bubbler by running a transfer line from the sample
bottle to the bubbler and opening the system to the atmosphere.
Attach the liMP nitrogen line to the sample bottle and allow the
pressure produced by the nitrogen to force 5 ml of the sample into
the bubbler. When the bubbler contains exactly 5 ml of the sample,
remove the nitrogen line, close the system, and remove the transfer
line.
9.3 Briefly open the system while separately injecting 5 p1 of the
surrogate standards (5.5) and 2 p1 of 3 percent antifoam solution
(5.6) into the sample. If excessive foaming occurs, the sample
extraction is repeated with 4 p1 of antifoam solution. Samples very
prone to foaming may require considerably higher levels of antifoam
solution.
9.4 Attach liMP nitrogen to the bubbler, open the system, and purge for
15 minutes at 30 mi/mm.
9.5 Remove the trap from the bubbler and attach one end of the trap to
the backflush and the other end to the GC, having the GC oven at
-30°C. Completely heat the trap and connectors to 200°C for 8
minutes while helium flows through the trap onto the column at 20
mi/mm.
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9.6 After desorbing remove the trap, attach the carrier gas to the GC
(20 mi/mm), and start the temperature program (50 to 220°C at
8°C/mm). Hold at 220°C for 16 minutes.
9.7 Acquire continuous mass spectral data throughout the chromatogram.
10. Identification and Quantification
10.1 Profile the extracted ion currents of the characteristic ions for
all determinate compounds in the composite standard; integrate the
areas.
10.2 Determine the relative percentages of the characteristic ions.
10.3 Identify the determinate compounds in a sample by comparing the
GC/MS data for the sample with the GC/NS data for the standards.
The presence of a compound is confirmed by the occurrence of its
characteristic ions at the predicted retention time (+ 1 mm) in the
correct relative percentages (+ 20 percent). Table 6 lists the
typical retention times, characteristic ions, and their relative
intensities. If the concentration of a pollutant is so great in a
sample that the extracted ion profile of the major characteristic
ion cannot be determined accurately, a secondary characteristic ion
may be used for quantification. However, analysts must be wary of
the mass spectrometer becoming saturated by large amounts of organic
compounds.
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TABLE 6. GC/MS CHARACTERISTICS OF VOLATILE ORGANIC POLLUTANTS
Retention Time
in Scan Numbers
Characteristic Ions
(% Relative Intensity)
benzene
194
78(100)
bromoform
221
173(100) ,171(50) ,175(50)
carbon tetrachioride
137
119(l00),lll(99),121(30)
chlorobenzene
314
112(100),114(30)
chiorodibromomethane
181
129(100),127(80),208(15)
chloroform
102
83(100),85(65)
dichlorobromomethane
141
83(100) ,86(65) ,127(1O)
1,1-dichioroethane
89
63(100),65(30),83(15)
1,2—dichioroethane
114
62(100) ,64(40),98(35)
ethylbenzene
344
91(lOO),106(35)
methylene chloride
52
84(100) ,51(60) ,49(55)
tetrachioroethane
260
83(100) ,85(70),168(20)
l,1,2,2-tetrachloroethy lene
274
166(100) ,164(75),129(50)
toluene
299
91(100),92(55)
1,1,1—trichioroethane
129
97(l0O),99(70),117(20)
trichloroethylene
182
130(100) ,95(70),97(20)
trichlorofluoromethane
73
101(100) ,103(60)
xylenes
400
91(100) ,106(50) ,105(20)
-21-
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10.4 When the GC/MS data for a sample meets the above criteria for detec-
tion, the concentration (Cs) is calculated as follows:
= (A) (C) (voluin: correction factor)
A = Integrated peak area from the characteristic ion
X plot of the pollutant in the sample.
A = Integrated peak area from the characteristic ion
S plot of the pollutant in the standard.
Cs = Concentration of pollutant in the standard.
10.5 Report results in ng/ml of sample water.
—22—
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SECTION III
ANALYSIS OF SENIVOLATILE ORGANIC POLLUTANTS PRESENT IN
PULP, PAPER, AND PAPEREOARD INDUSTRY WAS TEWATERS
1. Scope and Application
1.1 This procedure is suitable for GC/MS determination of at least 33
semivolatile organic toxic and nonconventional pollutants which are
amenable to organic extraction and gas chromatographic resolution.
1.2 Compounds that have been determined by this method are listed in
Table 7.
1.3 This method is applicable to the determination of these compounds in
pulp, paper, and paperboard industry wastewaters, and may be exten-
ded to other pollutants which are amenable to liquid-liquid extrac-
tion of wastewaters.
1.4 The sensitivity of the method is usually dependent upon the level of
interferences rather than instrumental limitations. The limits of
detection listed in Table 8 represent sensitivities that can be
achieved in wastewaters under optimum operating conditions.
1.5 This method is recoimuended for use only by experienced GC/MS anal-
ysts or under the close supervision of qualified persons.
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TABLE 7. TOXIC AND NONCONVENTIONAL POLLUTANTS APPLICABLE FOR
GC/NS SENIVOLATILE ORGANIC ANALYSIS
abietic acid isopimaric acid
acenaphthylene isophorone
anthracene linoleic acid
bis (2-ethyihexyl )phtha late linolenic acid
butyl benzyl phthalate . inonochiorodehydroabietic acid
2- ch].orophenol naphthalene
chrysene oleic acid
dehydroabietic acid para-chioro-meta-cresol
dichiorodehydroabietic acid pentachiorophenol
2, 4-dichiorophenol phenanthrene
9,10-dichiorostearic acid pimaric acid
diethyl phthalate pyrene
2, 4-dinitrophenol phenol
di-n-butyl phthalate tetrachiorogualacol
di-n—octyl phthalate 3 ,4,5—trichloroguaiacol
9, ].O-epoxystearic acid trichlorophenol*
fluoranthene
*Includes 2,4,5-trichiorophenol and 2,4, 6-trichlorophenol
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TABLE 8. TYPICAL DETECTION LIMITS FOR SEMIVOLATILE ORGANIC POLLUTANTS
Limit of Detection
Compound (pg/i)
TNS-abietic acid 30
acenaphthene 10
acenaphthy lene 10
anthracene 10
bis (2-ethylhexyl)phthalate 1
butyl benzyl phthalate 5
TMS-2-ch loropheno l 5
chrysene 10
TMS-dehydroabietic acid 10
TNS-dichlorodehydroabietic acid 50
TNS-2 , 4-dichiorophenol 5
TNS-9,10—dichlorostearic acid 100
diethyl phthalate 5
TNS-2,4 dinitrophenol 1 mg/i
di-n-butyl phthalate 1
di—n-octyl phthalate 1
TNS-9,10-epoxystearic acid 100
fluoranthene 10
TMS—isopimaric acid 30
isophorone 100
TMS-linoleic acid 50
TNS—linolenic acid 50
TNS-monochlorodehydroabietic acid 40
naphtha lene 10
TMS—oleic acid 50
TMS- -ch1oro-rn -creso1 5
TNS-pentach lorophenol 5
TMS-pheno l 5
TNS-pimaric acid 30
pyrene 10
TMS-tetrach loroguaiacol 10
TMS-3,4,5-trich loroguaiaco l 10
TMS -trich loropheno l* 5
*Includes TNS-2,4,5-trichlorophenol and TMS—2 ,4,6-trichlorophenol
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2. Summary of Method
2.1 A one liter sample of wastewater is acidified to a pH of 2 or less
and extracted with methylene chloride. The extractions are done
using separatory funnel techniques. The resulting acid-neutral
extract is dried with anhydrous sodium sulfate and concentrated
using a Kuderna—Danish evaporation to a volume of 1 ml. Derivatiza-
tion with MSTFA (10.1, 10.2) is performed. GC/MS conditions are
described which allow for the measurement of the compounds in the
extract.
3. Interferences
3.1 Solvents, reagents, glassware, and other sample processing hardware
may result in the introduction of organic compounds (i.e., phthal-
ates) and cause a misinterpretation of GC/MS data. All of these ma-
terials must be demonstrated to be free from interferences under the
conditions of the analysis by running method blanks. Specific
selection of reagents and purification of solvents by distillation
in an all glass systems may be required.
3.2 Interferences will vary considerably from source to source, depend-
ing on the diversity of the industrial effluents. General cleanup
techniques are not given as part of thia method; unique samples may
require special cleanup procedures prior to analysis to achieve the
sensitivities listed in Table 8.
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4. Apparatus and Materials
4.1 Sampling equipment for discrete or composite sampling:
4.1.1 Sample bottle, glass, one-liter volume minimum. The French
or Boston Round design is recommended. The container must
e
be washed and rinsed with solvent before use to minimize
interferences.
4.1.2 Bottle caps-—threaded to fit on bottles. The caps must be
lined with Teflon.
4.1.3 Compositing equipment--The automatic or manual compositing
system must incorporate glass sample containers are kept
iced or refrigerated during sampling. No tygon or rubber
tubing or fittings should be used in this system.
4.2 Separatory funnel--2000 ml with Teflon stopcock.
4.3 Drying colunin--20 nun ID Pyrex chromatographic column with coarse
frit.
4.4 Kuderna-Danish (K-D) Apparatus
4.4.1 Concentrator tube--lO ml graduated (Kontes K-570050-l025 or
equivalent). Calibration must be checked. Ground glass
stopper (size 19/22 joint) is used to prevent evaporation of
extracts.
4.4.2 Evaporative flask--500 ml (Kontes K-57001-0500 or equiva-
lent). Attach to the concentrator tube with springs (Kontes
K-662750-0012 or equivalent).
-27-
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4.4.3 Snyder column--three-ball macro (Kontes K-570000-0250 or
equivalent).
4.4.4 Snyder column--two-ball micro (Kontes K-569001-0219 or
equivalent).
4.4.5 Boiling chips--approximately 10/40 mesh.
4.5 Water bath-—heated, with concentric ring cover, capable of tempera-
ture control (+ 2°C). The bath should be used in a hood.
4.6 Gas chromatograph/mass spectrometry system--complete with a pro-
grammable gas chromatograph and all required accessorIes including:
column supplies, recorder, gases, and syringes. A computerized data
system capable of storing continuous mass spectral data and of
integrating extracted ion profiles is required. (Hewlett Packard
5985 GC/MS with HP21 IIX E-series data system or equivalent)
4.7 Chromatographic column-—50 m SE-30 SCOT capillary, Neff >50,000.
4.8 Reaction vial--with Teflon-lined screw caps, 1 ml.
4.9 Storage vial--5 or 10 ml serum vial with Teflon-lined caps.
4.10 Syringes--i p1, 25 p1, 250 p1, and 1 ml.
5. Reagents
5.1 Preservatives.
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5.1.1 SodIum hydroxide--(ACS) 10 N in distilled water.
5.1.2 Hydrochloric acid-—(ACS).
5.2 Methylene chloride-—Pesticide quality or equivalent.
5.3 Sodium sulfate-—(ACS) granular, anhydrous (purified by heating at
400°C for 4 hrs).
5.4 Nonconventional pollutant standards.
5.4.1 Abietic acid, dehydroabietic acid, isopimaric acid, mono—
chlorodehydroabietic acid, 3 ,4,5-trichloroguaiacol, tetra-
chloroguaiacol, 9,10-dichiorostearic acid, and dichiorode-
hydroabietic acid standards - (B.C. Research, Vancouver,
Canada V652L2).
5.4.2 Pimaric acid standard—-(Chemical Procurement Labs, College
Point, New York 11356).
5.4.3 9,10-epoxystearic acid standard--(ICN K&K Laboratories,
Inc., Plainview, New York 11803).
5.4.4 Oleic acid, linoleic acid, and linolenic acid standards -
(Sigma Chemicals, St. Louis, Missouri, 63178).
5.5 Stock standards solutions are prepared for each chemical class of
pollutants at a concentration of 1.00 pg/pl by dissolving 0.100
grams of assayed reference material (all compounds of interest
including surrogate standards and internal standard) in pesticide
quality methylene chloride. Dilute to volume in a 100 ml ground
glass stoppered volumetric flask. The stock solution is transferred
—29—
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to ground glass stoppered reagent bottles, stored in a refrigerator,
and checked frequently for signs of degradation or evaporation,
especially just prior to preparing working standards from them.
5.5.1 Working standards--Combine stock standards and adjust the
volume to achieve 200 ng/pi of each compound assayed.
Working composite standards are prepared each month and a
portion of the working standard is derivatized each week for
daily analysis.
5.6 Surrogate standards--Prepare a spiking solution at the following
concentrations:
phenol-d 5 0.2 mg/mi
naphthalene-d 8 0.2 mg/nil
diamyl phthalate 0.2 mg/nil
stearic acid-d 35 0.4 mg/nil
Dissolve 0.200 grams (0.400 g of stearic acid-d 35 ) of the standards
in pesticide quality methylene chloride and dilute to volume in a
100 ml ground glass stoppered volumetric flask. The standard solu-
tion is transferred to 15 ml vials with Teflon-lined seals and
stored at -20°C.
5.7 Internal standard: Prepare standard solution, 10 mg/nil, by dis-
solving 20 nig of anthracene-d 10 (KOR Isotopes, Cambridge, Nassa-
chusettes) in pesticide quality methylene chloride and diluting to
volume in a 2 ml ground glass stoppered volumetric flask.
-30-
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5.8 N-methyl-N—triinethylsilyltrifluoroacetamjde (MSTFA)--Derivatizing
reagent (Pierce Chemical, Rockford, Illinois, 61105).
5.9 Decafluorotriphenyl phosphine (DFTPP)--MS tuning compound (PCR,
Inc. Gainesville, Florida).
5.10 Perfluorotributylamine (PFTBA)--NS tuning compound (PCR, Inc.,
Gainesville, Florida).
6. Calibration
6.1 Tune the mass spectrometer according to the manufacturer’s specifi-
cations with PFBTA; verify the spectrum of DFTPP according to the
published guidelines (2). Analytical GC/MS parameters are given in
Table 9.
6.2 Derivatize 100 p1 of the working composite standard (5.4.1 and 10).
After cooling the reaction vial analyze 1 p1 according to the pro-
cedure given in section 11.
6.3 After the GC/MS run is completed, integrate the areas of the charac-
teristic ions of each compound in the standard.
Determine the relative retention time (RT), relative response
ratio (RR), and relative percentages of the characteristic ions for
each compound:
—31—
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TABLE 9. GC/MS SEMIVOLATILE ORGANIC ANALYSIS PARAMETERS
Extraction Conditions
1 liter sample (pH 10 or greater)
Adjust pH 2 or less
Spike with surrogate standards (200 to 400 ppb)
Serial extraction with methylene chloride (125 x 50 x 50 ml)
Break emulsions by glass wool filtration or solvent addition
Dry methylene chloride with sodium sulfate
Concentrate sample by Kuderna-Danish evaporation to 1.0 ml
Add 100 rig/vial anthracene-d 10
Store sample in 5.0 ml serum vial with Teflon/rubber septum
Mass Spectrometer - HP 5985
amu range: 33-450
Scan speed: 300 amu/sec
A/D per 0.1 amu: 3
Gas Chromatograph - HP 5840
Column: 50 m SE-30 SCOT, (SGE D grade >50,000 Neff)
Flow rate: 22 cm/sec at 200°C
Injection volume: 1 p1, splitless injection
Temperature program: 30 to 260°C at 6°/C/mm
-32-
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scan number of A
RT= x
scan number of A
( As) (Cr )
(Ar) (Cx)
A = Integrated peak area from the characteristic ion
plot of the pollutant.
Ar = Integrated peak area from the characteristic ion
plot of the reference standard (anthracene-d 10 ).
C = Amount of pollutant injected into the GC/MS system.
Cr = Amount of anthracene’-d 10 injected into the GC/MS system.
7. Quality Control
7.1 Before processing any samples, the analyst should demonstrate,
through the analysis of a distilled water method blank, that all
glassware and reagents are free from interference. Each time a set
of samples is extracted or when there is a change in reagents, a
method blank should be processed to identify any chronic laboratory
contamination.
7.2 Standard quality assurance practices should be used with this meth-
od. Field blanks should be collected to validate the sampling,
storage, and analysis process. Laboratory blanks should be analyzed
to validate the integrity of the analysis.
7.3 Samples should be spiked with surrogate standards to validate the
accuracy of the analysis. Table 10 lists the surrogate standards.
By adding these standards to each sample analyzed, it is possible to
assess system performance on a per-sample basis. Once the GC/MS
-33-
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TABLE 10. SEMIVOLATILE ORGANIC ANALYSIS SURROGATE STANDARDS
phenol-d 5
naphthalene-d 3
diamyl phthalate
stearic acid-d 35
-34-
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analysis is completed, the extracted ion currents of the character-
istic ions of the surrogate standards are profiled. The area of the
characteristic ion for the internal standard (5.7) should be inte-
grated. If the value is within ±50 percent of the area obtained for
the interal standard alone, and the peak shape of all characteristic
ions are at least 90 percent Gaussian, the analysis can be con-
sidered valid.
7.3.1 The areas of the characteristic ions of each surrogate
standard should be integrated; if the recovery of the
surrogate standards on any sample varies by more than two
standard deviations from the norm expected, the sample
should be re-extracted and re-analyzed.
7.3.2 The peak shape of the characteristic ions are required to
be at 90 percent Gaussian for a valid analysis.
7.4 The linearity of the system should be checked monthly over the range
of concentrations commonly encountered in sample analyses. The
composite standard in various dilutions can be used for GC/MS line-
arity checks.
8. Sample Collection, Preservation, and Handling
8.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed. Composite samples should be
collected in iced or refrigerated glass containers in accordance
with the requirements of the program. No tygon or other material
which might lead to contamination should be used in the automatic
sampling equipment.
-35-
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8.2 The samples should be iced or refrigerated from the time of collec-
tion until extraction. At the sampling location, fill the glass
container with sample. Adjust the sample pH to 10±0.2, as measured
by pH meter, using sodium hydroxide. If sample pH is greater than
10±0.2 at time of collection, do not adjust downward. Record the
volume of sodium hydroxide used on the sample identification tag.
8.3 All samples must be extracted within 7 days and completely analyzed
within 30 days of collection.
9. Sample Extraction
9.1 Transfer one liter of the sample into a two liter separatory funnel;
add 1 ml of the surrogate standard solution (5.5). Adjust the
sample to a pH of 2 or less with hydrochloric acid (5.1.2).
9.2 Add 60 ml methylene chloride to the graduated cylinder and rinse.
Transfer the rinse solvent and 65 ml more methylene chloride into
the separatory funnel and extract the sample by shaking the funnel
for 2 minutes with venting periodically to release vapor pressure.
Allow at least 10 minutes for the organic layer to separate from the
water phase. If an emulsion interface forms between the layers, the
analyst must employ mechanical techniques to complete the phase
separation. The optimum technique depends on the sample, but may
include stirring, filtering the emulsion through glass wool, or
adding solvent. Collect the inethylene chloride layer, and repeat
the sample extraction with two additional 50 ml portions of methy-
lene chloride in the same manner.
-36—
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9.3 Combine all fractions of methylene chloride (rinses and extracts).
Filter extract through a drying column containing 3-4 inches of
anhydrous sodium sulfate, and collect it in a 500 ml Kuderna-Danish
flask equipped with a 10 ml concentrator tube. Rinse the Erlenineyer
flask and column with 20-30 ml of methylene chloride to complete the
quantitative transfer.
9.4 Add 1-2 clean boiling chips to the flask and attach a three-ball
macro-Snyder column. Prewet the macro-Snyder column by adding about
10 ml of methylene chloride to the top. Place the Kuderna-Danish
apparatus on a steaming hot (60-65°C) water bath so that the concen-
trator tube is partially immersed in hot water, and the entire lower
rounded surface of the flask is bathed in steam. Adjust the verti-
cal position of the apparatus and the water temperature as required
to complete the concentration in 15-20 minutes. At the proper rate
of distillation, the balls of the column will actively chatter but
the chambers will not flood. When the apparent volume of liquid
reaches 1 ml, remove the Kuderna-Danish apparatus and allow it to
drain for at least 10 minutes while cooling.
9.5 Remove the receiver of the Kuderna-Danish, add fresh boiling chips,
attach a two-ball micro—Snyder column, and carefully evaporate
until approximately 0.5 ml remains: Remove the micro-Snyder column
and rinse its lower joint into the concentrator tube with a minimum
of methylene chloride. Adjust the extract volume to exactly 1.0 ml.
Add 10 .al of the internal standard, anthracene—d 10 (5.7). Store in
5 ml vials with Teflon-lined caps at -20°C until analysis.
—37—
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10. Derivatizatjon
10.1 Transfer 100 p1 of extract to a 1 ml reaction vial; add 50 p1 of
FISTPA.
10.2 Heat at 70°C for 15 miii. Allow extract to cool before opening
reaction vial.
11. GC/MS Analysis Techniques
11.1 The GC/NS analysis conditions are given in Table 9. Inject 1 p1 of
derivatized extract with the oven temperature at 30°C. Hold at 30°C
for one minute then program the GC temperature to rise to 260°C at
6°C/mm.
11.2 After the solvent front and excess MSTFA are eluted (approximately
11 miii) collect continuous mass spectral data throughout the chroma-
togram until the last compound of interest has eluted.
12. Identification and Quantification
12.1 Identify the compounds of Interest in a sample by comparing the
GC/NS data for the sample with the GC/MS data for the composite
standard analyzed that day. The presence of a compound is confirmed
by the occurrence of its characteristic ions at the predicted reten-
tion time (+ 1 miii) in the correct relative percentages (+ 20 per-
cent) (6.3). Table 11 lists the relative retention times, charac-
teristic ions, relative intensities, and typical response ratios of
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TABLE 11. GC/MS CUARACTERISTICS OF SEMIVOLATILE ACID-NEUTRAL EXTRACTABLE POLLUTANTS
Relative
Relative
Retention
Response
Characteristic Ions
Compound Time
Ratio
(% Relative Abundance)
TMS-abietic acid
a cenaphthene
acenaphtby lene
anthracene
bis (2-ethy lhexyl)phtha late
butyl benzyl phthalate
TMS-2-chlorophenol
chrysene
TMS-dehydroabietic acid
TMS-dichlorodehydroabietic acid
TMS-2 , 4 dichiorophenol
TMS-9,10-dicblorostearic acid
dfethyl phthalate
TMS-2 ,4-dinitrophenol
di-n-butyl phthalate
di-n-octyl phthalate
TMS-9, LO-epoxystearic acid
epoxystearic acid
fluoranthene
TMS-isopimaric acid
isophorone
TMS-linoleic acid
TMS-linolenic acid
TNS-monochlorodehydroabietic acid
naphthalene
ThS-oleic acid
TMS- -chloro-rn-cresol
TtIS -pentachiorophenol
ThS-phenol
TMS-pimaric acid
pyrene
TMS - te t ra chlo rogua i a cal
TMS-3 ,4 ,5-trichloroguaiacol
THS - t ri chloropheno 1*
256(100) ,241(52) ,257(30)
154(lOO), 153(86)
152 (100) , 151(20)
178(100) ,177(15) ,179(lO)
149 (100) , 167 (40)
91(100) ,l49(89) ,206(21)
185(lOO),149(75) ,200(30)
228(100) ,226(21) ,229(21)
239 (100) 240(21)
307(l00),309(7 0)
93(100) ,219(88),221(62)
117(100) ,132(47) ,129(55)
149(100) ,177(23)
241(100), 195 (26)
149(100) ,150(11)
149(100) ,279(23)
75(100),117(49) ,155(25)
155 (100) 337 (40)
202(100) ,200(10)
241(100) ,256(76) p257(35)
82(100) ,138(30)
337(100) ,150(35) ,262(41)
108(100) ,335(14)
273(100) ,275(30)
128(100) ,127(10) ,126(10) ,129(.L0)
339(100) ,246(10)
199(100) ,214(50) ,201(40)
323(100) ,325(62)
151(100) ,166(36)
121(100) ,120(63),257(32)
202(100) ,200(16)
304(100) ,302(70) ,306(50)
270(100),268(82) ,272(34)
253(100) ,255(85)
1.630
0.610
0.575
1.002
1.732
1.571
0.238
1.685
1.602
1.934
0.462
1.811
0.768
0.905
1.182
1.899
1.629
1.629
1.303
1.563
0.130
1.451
1.457
1.762
0.204
1.. 461
0.408
1.089
0.067
1.538
1.397
1.049
0.973
0.625
0.230
1.355
1.602
1.506
1.691
0.986
0.911
1.294
1.024
0.089
0.671
0.074
1.092
2.000
3.814
2.479
0.213
0.080
1.598
0.512
1.138
0.107
0.145
0.221
2.224
0.108
1.265
0.156
1.676
0.324
2.021
0.433
0.539
0.446
*Includes 2,4,5-trichlorophenol and 2,4,6-trichlorophenol
-------
the pollutants determined. If the concentration in a sample is so
great that the extracted ion profile of the major characteristic ion
cannot be determined accurately, a secondary characteristic ion may
be used for quantification. However, analysts must be wary of the
mass spectrometer becoming saturated by large amounts of organic
compounds.
12.2 When the GC/HS data for a sample meet the above criteria for detec-
tion, the concentration (C) is calculated as follows:
c = (Cr) (volume correction factor )
(Ar)
= The integrated peak area from the characteristic
plot of the pollutant.
Ar = The integrated peak area from the characteristic ion
plot of the internal standard.
C The concentration of the internal standard.
r
RH = The relative response ratio determined from the daily
analysis of the composite standard (see 6.3).
12.3 Report results in parts per billion uncorrected for recovery.
13. Recovery of Surrogate Standards
13.1 The extraction efficiency of each analysis can be monitored by
quantifying the concentration of the surrogate standards according
to Section 12.
-40-
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13.2 The percent recovery is calculated as follows:
X 100 —
[ Cisi —
EC 15 l The concentration of the surrogate standard added
to the sample.
[ C 1 5 ] ’ = The concentration of the surrogate standard found
in the sample extract.
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14. References
1. Bellar, T.A., and J.J. Lichtenberg. “Journal of the American Water
Works Association,” 66(12) :739—1974.
2. “Base/Neutrals, Acids, and Pesticides - Method 625, “ Federal Regis-
ter, Vol. 44, No. 233. Monday, December 3, 1979, p. 69540.
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BIBLIOGRAPHY
1. Abrahamsson, S., F.W. McLafferty, E. Stenhagen. Registry of Mass Spec-
tral Data , John Wiley and Sons, New York, 1974.
2. Bellar, T.A., and J.J. Lichtenberg, Journal American Water Works Asso-
ciation , 66(12):739, December 1974.
3. Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants , Environmental Protection Agency, Cincinnati,
Ohio, March 1977, revised April 1977.
4. Analytical Methods for the Verification Phase of the BAT Review , Environ-
mental Protection Agency, Cincinnati, Ohio, June 1977.
5. Pierce, Alan E. “Silylation of Organic Compounds,” Pierce Chemical
Company, Rockford, Illinois, 1968.
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