United Statn
Environrnonttl Protection
Agency
Of flee of Water and
Warn Management
Washington. DC 20460
SW-846
Revision B
July 1981
Solid Waite
Test Methods
for Evaluating Solid Waste
Physical/Chemical Methods
Technical
Update
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U.S. Environmental Protection Agency
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TEST METHODS FOR EVALUATING SOLID WASTE
PHYSICAL/CHEMICAL METHODS
Technical Update
This manual (SW-846B) updates the Test Methods for Evaluating
Solid Waste (SW-846), and was written by the Hazardous and
Industrial Waste Division of the Office of Solid waste.
U.S. ENVIRONMENTAL PROTECTION AGENCY
July 1981
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This publication (SW-846B) is the second revision to Test Methods for
Evaluating Solid Waste (SW-846). Any mention of commercial products in
the manual or this revision does not constitute''endorsement by the U.S.
Government. Editing and technical content were the responsibilities of
the Hazardous and Industrial Waste Division, Office of Solid Waste.
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PREFACE
Attached is the second revision, dated April 15,1981, to the
Environmental Protection Agency's manual, Test Methods for Evaluating
Solid Waste (SW-846).
These attached pages should be inserted in the manual in place
of like-numbered pages or as entirely new pages, where appropriate.
The date on which the page was issued is printed in the upper right-hand
corner. Modified sections are indicated in the contents by double
underscores.
The Office of Solid Waste encourages comments and suggestions for
improving the utility or content of this manual. Comments may be made
by telephoning 202-755-9187 or writing:
Manager, Waste Analysis Program
Office of Solid Waste
U.S. EPA (WH-562)
Washington, DC 20460
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Revision B 4/15/81
Table of Contents
Section
Introduction
1.0 Evaluation Plan Design
2.0 Chain of Custody Considerations
3.0 Sampling Methodology
3.1 Sampling Plan Design [Reserved]
3.2 Sampling Equipment
3.3 Sample Containers
3.4 Sample Handling & Preservation [Reserved]
4.0 Ignitability (40 CFR 261.21)
5.0 Corrosivity (40 CFR 261.22)
6.0 Reactivity (40 CFR 261.23)
7.0 Extraction Procedure Toxicity (40 CFR 261.24)
7.1 Regulations
7.2 Separation Procedure
7.3 Sample Size Reduction [Reserved)
7.4 Structural Integrity Procedure
7.5 Extractors
8.0 Analytical Methodology
Gas Chromatographic Methods
8.01 Volatile organics, general
8.02 Volatile aromatics, selected ketones 6 ethers
8.03 Acrolein, Acrylonitrile and Acetonitrile
8.04 Phenols
8.06 Semi-volatile organics, not otherwise specified
8.08 Organochlorine pesticides and PCBs
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Revision B 4/15/81
8.09 Nitroaromatics
8.10 Polynuclear Aromatic Hydrocarbons
8.11 Haloethers [Reserved]
8.12 Semi-volatile chlorinated hydrocarbons, Not Otherwise
Specified
8.13 Chlorinated Dibenzo-p-dioxins [Reserved]
8.22 Organophosphorus pesticides
8.40 Chlorophenoxy acid pesticides
Gas Chromatographic/Mass Spectroscopy Methods
8.24 Volatile organics
8.25 Semi-volatile organics
8.27 Capillary Column GC/MS Metod for the Analysis of Wastes
High Performance Liquid Chromatographic Methods
8.30 Polynuclear Aromatic Hydrocarbons [See method 8.10]
8.32 Carbamates [Reserved]
Atomic Absorption Spectrographic Methods
8.49 General Requirements
8.50 Antimony
8.51 Arsenic
8.52 Barium
8.53 Cadmium
8.54 Chromium
8.55 Cyanide
8.56 Lead
8.57 Mercury
8.58 Nickel
8.59 Selenium
8.60 Silver
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Revision B 4/15/81
Other Measurement Methods
8.55 Titrimetric Method for Cyanide
8.56 Microcoulometric Method for Total Organic Halide
8.57 Titrimetric Method for Sulfides
Sample Preparation/Introduction Techniques
8.80 Direct Injection
8.62 Headspace
8.83 Purge and Trap
8.84 Shake Out
8.85 Sonication
8.86 Soxhlet Extraction
9.0 Interference Removal Procedures
9.01 Liquid - Liquid Extraction
10.0 Quality Control/Quality Assurance
11.0 Suppliers
Appendices
I "Samplers and Sampling Procedures for Hazardous Waste
Streams", EPA-600/2-80-018
II Selected sections of "Methods for Chemical Analysis
of Water and Wastes", EPA-600/4-79-020,
III "Methods for Benzidine, Chlorinated Organic
Compounds, Pentachlorophenol and Pesticides in Water and
Wastewater"
IV Selected sections from the Federal Register, "Guidelines
Establishing Test Procedures for the Analysis of Pollutants;
Proposed Regulations", 44 PR 69464-69567.
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Revision B 4/15/81 -8."27-1
Method 8.27
Capillary Column GC/MS method for the analysis of Wastes
Scope and Application
This method may be used to determine the presence and
concentration of the volatile and extractable organic compounds
which are listed in Appendix VIII, 40 CFR 261.33 in wastes. The
method employs capillary column gas chromatography-mass
spectrometry. Quantitation can be performed in two ways depending
on the level of information required.
Summary of Method
The waste is categorized by its physical makeup into one
of the following three classes.
0 Liquid (either single or multi-phase systems)
0 Solid
0 Combination of Liquid and Solid
Liquids are analyzed in their "as received" form except that
if more than one phase is present the organic and aqueous phases
are separated and the two phases analyzed separately. The
organic phases are analyzed by direct injection onto the
capillary column using, either the split or splitless technique.
Aqueous phases are de/termined by a combination of the purge
and trap technique for volitiles and a series of extractions
for the base/neutrals and acids. The extracted fractions
are then combined and analyzed as a single solution using
the splitless technique.
Solids are analyzed using purge and trap technique for
volatiles and a soxhlet extraction for the extractables.
Samples containing both liquid and solid phases are first
separated into their component liquid and solid phases
using centrifugation. The separated phases are then analyzed
as either liquids or solids as described above.
The components of the sample are quantitated in either
of two ways, depending on the degree of quantitation necessary.
The first way estimates concentration and assigns these
estimated concentrations into ranges. Since this is not a
rigorous quantitative procedure it may only be used for
order of magnitude type estimates of concentration. These
ranges are:
Greater than 50%
•Between 10 and 50%
Between 1 and 10%
Between 100 ppm and 1%
Between 1 and 100 ppm
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Revision B 4/15/81 8.27-2
For determining the precise concentration of a component in a
sample the method of standard additions is employed.
Procedure
The analyst must first determine which category the
sample belongs to.
0 If the sample is a liquid go to the section labled
"Liquids" (1} of this procedure.
0 If the sample is a solid go to the section labled
"Solids" (II) of this procedure.
0 If the sample contains both liquid and solid go to
the section labled "Mixtures of Liquids and Solids"
(III) of this procedure.
I, Liquids
The analyst should determine if more than one liquid
phase is present in the sample. If more than one phase is
present the sample should be separated into its organic and
aqueous phases respectively. This separation can be achieved
by using either gravity or cenrifugation. The separated
phases should be weighed. 10.0 gm of well mixed sample
should be used.
A. Organic Liquids
1. Summary
Organic Liquids are injected directly onto the
capillary column using either the split or splitless
mode. The liquid may be diluted if necessary to
facilitate sample handling or to accomodate the
linear range of the mass spectrometer.
2. Apparatus and Materials
a. Sample Vials - 10 dram vials with teflon lined caps
b. Gas Chromatograph - Analytical system capable of
split and splitless injections and all required
accessories including column supplies, gases, etc.
c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
.2 to .25mm internal diameter with a film thickness
between .15 to .40u.
d. Mass Spectrometer - Capable of scanning from 35 to
450 daltons every 1 second or less. The mass-
spectrometer must be able to operate at 70
volts for electron ionization and must produce
a recognizable mass spectrum for 50 ng or less
of DFTPP when the sample is introduced through
the GC column. The GC column should be directly
interfaced (i.e. no separator) to the mass
spectrometer through either an all glass or all
glass lined system. If a fused silica capillary
column is used, the analyst is required to
complete the interface by placing the end of
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Revision B 4/15/81 8.27-3
the column in the ion source.
e. Computer System - The computer system interfaced
to the mass spectrometer should be capable of
continuously acquiring mass spectra for the duration
of the gas chromatographic program, (about 1 hr.)
All data must be stored either within the data
system or on line mass storage devices such as
disk or tape. The system must have software
available capable of searching GC/MS runs for
the following:
1) selected ion chromatograms
2) total ion chromatograms
3) reverse and forward search for any compound
from the EPA/NIH Mass Spectral Data Base.
3. Reagents
a. Methylene chloride - Pesticide quality
b. Ethyl Ether - " "
c. Ethylacetate n "
d. Methanol - " "
e. Standards - Standards can be made up as necessary
if appropriate reagents are available. Naphthalene-dg
or phenanthrene-djo mav be used as internal standards.
4. Calibration
a. The mass spectrometer is calibrated with either
PFK or FC-43 oxver the scan range. The mass spec-
trometer should be scaned from 35 to 450 daltons
in 2 sec or less. 50ng or less of DFTPP should
be injected in the splitless mode using the
conditions given in Table 8.27-1.
b. The DFTPP spectrum obtained from the top of the
chromatographic peak (backgroud subtracted)
should meet the criteria listed in Table 8.24-2.
5. Sample Preparation
a. If the liquid can be convieniently drawn into a
10 ul syringe, then no sample preparation is
necessary. Weigh 1 gm of the liquid into a
a pre-tared 10 dram vial. Add the internal
standard at a level that would give 50 ng on
column when injected. (The amount added will
vary with split ratio)
b. If it is necessary to dilute the samplef a weighed
portion of the organic phase should be transfered
to an appropriate volumetric flask and diluted
to volume with one of the solvents listed in
the reagent section. The internal standard is
added at a level that would give 50 ng on column
when injected prior to dilution. Record the
dilution volume.
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Revision B 4/15/81 8.27-4
Gas Chromatography/Mass spectrometry
a. Establish the chromatographic conditions given
in table 8.27-1.
b. Set the Gas Chromatograph for either split
or splitless injection depending on estimated
concentration. For example, an organic liquid
that can be conveniently drawn up in a syringe
can be analyzed using the split mode. An oily
sample that needs to be diluted to 1:100 might
best be handled using the splitless mode. If
using the split mode, record the split ratio.
Record both linear and volume column flow.
c. Inject sample, start the chromatographic program,
and acquire data. Record amount of sample
injected. (1 to 5 ul when using split mode and
1 to 2 ul when the splitless mode is employed).
d. Inject appropriate standards and acquire data using
sample conditions as employed in c.
Qualitative and Quantitative Determination
a. A compound will be judged to have been identified
if either three or more characteristic ions of
the compound maximize within one scan of the
apex of the peak and the integrated ion areas
agree with a library or standard mass spectrum
within + 20%; or, a reverse search yields a numerical
value equivalent to the criteria stated above.
b. Samples can be quantitated in two ways. The first
is by the method of standard additions. This
method is always acceptable and must be used
when the actual concentration is needed. The
second method is used when order of
magnitude estimates of concentration are
needed. This is done by comparing the Total
Ion Chromatogram of the compound in the sample
with a standard. For example, if 100 ng of
benzene gives a total of 10,000 integrated area
counts then a peak corresponding to toluene
with 25,000 counts would be expected to correspond
to about 250 ng. When using this method the
analyst should try to use standards which resemble
the compounds in question as closely as possible.
The internal standard is used as a method check.
For example, if 50 ng of the internal standard
normally gives 5000 integrated area counts,
this condition should be met in the sample
+20%
c. Example Calculation
5 ul of a 5 rag/ml solution of benzene was injected
with a split ratio of 100:1 to produce the
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Revision B 4/16/31 C.27-5
chromatogram in figure 8.27-1. The integrated
area of the benzene peak from the total ion
chromatogram was 7840 counts. 10 gm of an
organic liquid sample was disolved in methylene
chloride in a volumetric flask to a final volume
of 100 ml. 5 ul of this solution was injected
with the same split ratio to produce the chromatogram
in figure 8.27-2. The integrated area for
benzene in this sample was 4235 counts. The
peak for toluene gave an area of 4827 counts.
The estimated concentration of benzene and
toluene in this sample are:
Benzene Standard
5 mg/ml = 5 ug/ul
5 ug/ul x 5 ul = 25 ug injected
7840 counts/25 ug = 313.6 counts/ug
Benzene in Sample
4235 counts/5 ul injected x 1 ug/ 313.6 counts =
13.5 ug/5 ul
13.5 ug/5 ul x 1000 ul/ml =
2700 ug/ml
2700 ug/ml x 100 ml/10 gm dilution = 27000 ug/gm
27000 ug/gm = 27 mg/gm
27 mg/gm x 1 gm/1000 mg = .027 = 2.7%
The sample is 2.7% benzene
Toluene in sample
By an analogus method the sample is calculated to
be 3.1% toluene.
8. Report
a. Report the results of each analysis giving
the method used to quantify each comound.
Report the scan number of each compound.
b. Example:
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Revision B 4/15/81 8.27-6
Compound Quantitation Scan Amount Range
Method #
Benzene Estimate/Benzene 500 2% 1-10%
Toluene Estimate/Benzene 622 3% 1-10%
B. Aqueous Liquid
1. S umma ry
Aqueous liquids are analyzed by purge and trap and
extraction methods given in Methods 8.83 and 8.84.
After the aqueous sample is purged and traped and
extracted by Methods 8.83 and 8.84 the traped material
and the extracts {which have been combined) are
analyzed by capillary column gas chromatography-mass
spectrometry.
2. Apparatus and Materials
See the appropriate sections in Methods 8.83, 8.84, and
the apparatus and materials section for organic liquids
in this method
3. Reagents
See the appropriate sections in Methods 8.83, 8.84, and
the reagents section for organic liquids in this method.
4. Calibration
a. The mass spectrometer is calibrated with PFK or
PC-43 over the scan range of interest. For the
volatiles scan over the range 20 to 260 daltons,
and scan over the range 35 to 450 daltons for
the base/neutrals and acid extractables. The
scan rates should be 2 sec. or less. 50 ng or
less of bromoflurobenzene or DFTPP should be injected
for the volitiles and extractables respectively.
Chromatographic conditions are given in Tables
8.27-2 and 8.27-3.
b. The specta obtained from the top of the chromatographic
peak (background subtracted) should meet the criteia
listed in Tables 8.24-2 and 8.24-3.
5. Sample Preparation
a. Follow the purge and trap and extraction methods
given in Methods 8.83 and 8.84 of this manual
for preparation of the sample.
b. Base/neutral and acid extractable fractions
may be combined and analyzed in a single GC/MS
analysis.
6. Gas Chromatography/Mass Spectrometry
a. Establish the Chromatographic conditions described
in Tables 8.27-2 or 8.27-3, whichever is appropriate.
b. Set gas chromatograph in either the split or
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Revision B 4/15/81 8.27-7
splitless mode. If using the split mode record
the split ratio. Record both the linear and
volume column flow.
c. When analyzing volatiles it may be necessary to
adjust desorption time or cool the first few
cm of the column with a flurocarbon spray
in order to maintain chromatographic resolution.
d. Inject sample and acquire data, recording the amount
injected. Follow the same procedure for any standards.
7. Quantitative and Qualitative Determination
a. A compound can be qualitativly identified in either
of two ways. At least three characteristic ions of the
compound must maximize within one scan of the apex
of the peak and the integrated ion areas agree with
a library or standard mass spectrum within ± 20%;
or, a reverse search yeilds a numerical value
equivalent to the criteria stated above.
b. Samples can be quantitated in two ways. The first
is by the method of standard additions. This
method is always acceptable and should be used
when the exact concentration is needed. The
second method is to be used only for order of
magnitude estimates of concentartion. This is
done by comparing the Total Ion Chromatogram of
the compound in the sample with a standard. For
example, if 100 ng of benzene gives a total of
10,000 integrated area counts then a peak corresponding
to toluene with 25,000 counts would be expected
to correspond to about 250 ng. When using this
method the analyst should try to use standards
which resemble the compounds in question as
closely as possible. The internal standard is used
as a method check. For example, if 50 ng of
the internal standard normally gives 5000 integrated
area counts, this condition should be met in
the sample +20%
c. Example Calculation
A 10 gm sample contained 3.5 gm of organic liquid
with a volume of 3.9 ml. 5 ul of the organic
liquid was injected with a split ratio of 100
to 1. The integrated area of benzene gave 3582
counts. Benzene in the organic phase is calculated:
3582 counts/5 ul x 1 ug/313.6 counts = 11.4 ug/5 ul
11.4 ug/5 ul x 1000 ul/ml = 2280 ug/ml
the density is 3.5gm/3.9ml = .9 gm/ml
2280 ug/ml = 2.28mg/ml
2.28mg/ml x Igm/lOOOmg x 1 ml/.9gm = .0025 = .25%
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Revision B 4/15/81 8.27-8
The purge and trap analysis of the aqueous phase
was performed on 6.5 gm of liquid. Benzene gave
12562 counts. The benzene in the aqueous phase
is:
12562 counts/6.5 gm x 1 ug/313.6 counts =
40.0 ug/6.5 gm = 6.2 ppm
This is insignificant compared to .25%
The total amount of benzene in the sample is
calculated:
.25% x .35 of total = .0875% or 875 ppm
8. Report
a. Report the results of each analysis giving
each compound identified, the scan number, the
quantity of the compound, and the method used
to calculate that quantity.
b. Example
Compound Quantitation Scan Amount Range
Method #
Benzene Estimate/Benzene 687 875ppm 100ppm-l%
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Revision B 4/15/81 8.27-9
II. Solids
Two samples of well mixed solid should be used in this
analysis. One sample is used for the purge and trap analysis
of volatiles and one for soxhlet extraction analysis.
A. Purge and Trap Determination of Volatiles in Solids
1. Summary
An appropriate weight of sample (1-10 gm) is diluted
with 10 ml of organic-free water. The diluted
sample is purged for 12 min. with inert gas at
room temperature. The gaseous phase is passed
through a sorbent trap where the organic compounds
are concentrated. The contents of the trap are
desorbed into the GC/MS by heating and backflushing
the trap.
2. Apparatus and Materials
a. See the apparatus section of Method 8.83 of this
manual.
b. Gas Chromatograph - Analytical system capable of
split and splitless injections and all required
accessories including column supplies, gases, etc.
c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
.2 to ,25mm internal diameter with a film thickness
between .15 to .40u.
d. Mass Spectrometer - Capable of scanning from 20 to
260 daltons every 1 second or less. The MS must
be able to operate at 70 volts for electron
ionization and must produce a recognizable mass
spectrum for 50 ng or less of BFB when the sample
is introduced through the GC column. The GC column
should be directly interfaced (i.e. no separator)
to the mass spectrometer through an all glass
or all glass lined system. If a fused silica
capillary column is used, the analyst is required
to complete the interface by directly connecting
the end of the column to the ion source.
e. Computer System - The computer system interfaced
to the mass spectrometer should be capable of
continuously acquiring mass spectra for the duration
of the gas chromatographic program, (about 1 hr.)
All data must be s,tored either within the data
system or on line mass storage devices such as
disk or tape. The system must have software
available capable of searching GC/MS runs for
the following:
1} selected ion chromatograms
2) total ion chromatograms
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Revision B 4/15/81 8.27-10
3) reverse and forward search for any compound
from the EPA/NIH Mass Spectral Data Base
3. Reagents - Standards as necessary (See Methods 8.24,
8.83, and I-A-3e of this Method)
4. Calibration
a. The mass spectrometer is calibrated with either
PFK or FC-43 over the scan range. 50ng or less of
BFB should be injected in the splitless mode
using the conditions given in table 8.27-3.
b. The spectrum obtained from the top of the chro-
matographic peak (backgroud subtracted) should
meet the criteria listed in table 8.24-2.
5. Sample Preparation
a. Weigh an appropriate sample into a pretared 10 to
15 ml Teflon lined, screw-capped vial.
b. Dilute the sample with 10 ml distilled water.
Disperse the sample into the water. Transfer
the total sample to the purging device using a
syringe with an 1/8 in. gauge Teflon needle.
Seal the sample in the purging device. Add
the internal standard and purge with 40
ml/min (He or N2) for 12 min. at room temperature.
6. Gas Chromatography/Mass spectrometry
a. Establish the chromatographic conditions given
in table 8.27-1.
b. Set up the Gas Chromatograph for either split
or splitless injection. If using the split
mode, record the split ratio, linear and volume
column flow.
c. The first few inches of the column should be
cooled using flurocarbon spray. Heat the trap
to 200°C. Backflush it for 4 min in the
desorb mode into the gas Chromatograph.
7. Qualitative and Quantitative Determination
a. A compound can be qualitativly identified in either
of two ways. At least three characteristic ions of the
compound must maximize within one scan of the apex
of the peak and the integrated ion areas agree with
a library or standard mass spectrum within _+ 20%;
or, a reverse search yeilds a value equivalent to
the criteria stated above.
b. Samples can be quantitated in two ways. The first
is by the method of standard additions. This
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Revision B 4/15/81 8.27-11
method is always acceptable and should be used
when the exact concentration is needed.
The second method is to be used only for order
of magnitude estimates of concentration as
given on page 1 of this method. This is done
by comparing the Total Ion Chromatogram of the
compound in the sample with a standard. For
example, if 100 ng of benzene gives a total of
10,000 integrated area counts then a peak corresponding
to toluene with 25,000 counts would be expected
to correspond to about 250 ng. When using this
method the analyst should try to use standards
which resemble the compounds in question as
closely as possible. The internal standard is
used as a method check. For example, if 50 ng
of the internal standard normally gives 5000
integrated area counts this condition should
be met in the sample ^20%.
Example Calculation
5.0 gm of a solid sample was mixed with 10 ml
water and purged and traped by the procedure
specified. A splitless injection gave 29,043
integrated area counts for toluene. 1 ul of
a standard solution of Toluene 100 ug/ml gave
16,290 integrated counts.
16290 counts/ 1 ul x 1000 ul/100 ug = 162900 counts/ug
29043 counts/5 gm x 1 ug/162900 counts = .18 ug/5 gm
.18 ug/5 gm = .036 ug/gm = .036 ppm
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Revision B 4/15/81 8.27-12
8. Report
a. Report the results of each analysis giving
each compound identified, the scan number, the
quantity of the compound, and the method used
to calculate that quantity.
b. Example
The level of toluene in the sample is very low
and for the purpose of this analysis is reported
at less than 1 ppm
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Revision B 4/15/81 8.27-13
B. Soxhlet Extraction for Solids
1. Summary
The sample is mixed with anhydrous sodium sulfate,
placed in an extraction thimble or between two
plugs of glass wool and extracted using methylene
chloride. The extract is reserved. The remaining
contents of the thimble are mixed with distilled
water and the pH is adjusted to 2 or less. This
aqueous mixture is extracted with ethyl ether.
The two extracts are dried, combined, and anaylzed
in one GC/MS analysis.
2. Apparatus and Materials
a. Soxhlet extractor - 40 mm id, with 500 ml round-
bottom flask.
b. Kuderna-Danish Apparatus [Kontes K-570000 or equivalent]
with 3-ball snyder column
c. Gas Chromatograph - Analytical system capable of
split and splitless injections and all required
accessories including column supplies, gases, etc.
d. Column - 30m SE-30, SE-52, SE-54, or equivalent,
.2 to .25mm internal diameter with a film thickness
between .15 to .40u.
e. Mass Spectrometer - Capable of scanning from 35 to
450 daltons every 1 second or less. The MS must
be able to operate at 70 volts for electron
ionization and must produce a recognizable mass
spectrum for 50 ng or less of DFTPP when the sample
is introduced through the GC column. The GC column
should be directly interfaced (i.e. no separator)
to the mass spectrometer through an all glass
or all glass lined system. If a fused silica
capillary column is used, the analyst is required
to complete the interface by directly connecting
the end of the column to the ion source.
f. Computer System - The computer system interfaced
to the mass spectrometer should be capable of
continuously acquiring mass spectra for the duration
of the gas chromatographic program, (about 1 hr.)
All data must be stored within the data system.
Mass storage devices such as disk or tape are
accepable. The system must have software available
to allow searching GC/MS runs for the following:
1) selected ion chromatograms
2) total ion chromatograms
3) reverse and forward search for any compound
from the EPA/NIH Mass Spectral Data Base
3. Reagents
a. Methylene chloride - Pesticide grade
b. Ethyl Ether - Pesticide grade
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Revision B 4/15/81 8.27-14
c. Anhydrous Sodium Sulfate, ACS grade, purified
by heating at 400 C for 4 hr. in a shallow tray.
4. Calibration
a. The mass spectrometer is calibrated with either
PFK or FC-43 over the scan range. 50ng or less of
DFTPP should be injected in the splitless mode
using the conditions given in table 8.27-1.
b. The DFTPP spectrum obtained from the top of the
chromatographic peak (backgroud subtracted)
should meet the criteria listed in table 8.24-2.
5. Sample Preparation
a. Blend 10.0 gm of the solid sample with 10.0 gm
of anhydrous sodium sulfate. Weigh this mixture
to the nearest 0.1 gm. Place in either a paper
(pre-washed with methylene chloride and dried)
or glass extraction thimble.
b. Place the thimble in the extractor. (If any
problems arise when using the thimble, i.e. if
the sample clogs the thimble, an alternative
would be to place a plug of glass wool in the
extraction chamber, transfer the sample into
the chamber, then cover the sample with another
plug of glass wool.)
c. Place 250 ml of methylene chloride into the 500 ml
roundbottom flask, add a boiling chip and attach
the flask to the extractor. Extract the sample
for 16 hours.
d. After the extraction is complete, cool the extract;
rinse extractor flask and thimble with fresh
solvent. Combine the extract and rinse.
Dry the extract by passing it through a 4 inch
column of sodium sulfate that has been washed
with solvent. Collect the dried extract
in a 500 ml Kuderna-Danish (KD) flask fitted with
a 10 ml graduated concentartor tube.
Empty the contents of the thimble into a pre-weighed
250 ml Erlinmeyer flask. Add 100 ml distilled
water to the flask.
e. Adjust the pH to 2 or less with sulfuric acid
solution. Extract three times with fresh 60 ml
portions of ethyl ether. Combine the three
extracts and dry by passing through a 4 inch
column of sodium sulfate. Rinse column with
fresh solvent. The dried extract is added to
the KD.
f. Evaporate the aqueous solution in the erlinmeyer
flask to dryness; cool the flask and weigh the
residue. Determine the weight difference between
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Revision B 4/15/81 8.27-15
the residue in the erlinmeyer flask and the
original sample.
g. Concentrate the dried extracts in the KD. A
level that would give a final concentration of
about 1 mg/ml is generally appropriate for
GC/MS.
h. The concentrated extract should be placed in a
volumetric flask and made up to the appropriate
volume.
Gas Chromatography/Mass spectrometry
a. Establish the chromatographic conditions given
in table 8.27-1.
b. Set the Gas Chromatograph for either split
or splitless injection. If using the split
mode, record the split ratio. Record both
liniar and volume column flow.
c. Inject sample and acquire data. Record amount
of sample injected. (2 to 5 ul for split
and 1 to 2ul for splitless)
d. Inject appropriate standards and acquire data as
in c.
Qualitative and Quantitative Determination
a. A compound can be qualitativly identified in either
of two ways. At least three characteristic ions of the
compound must maximize within one scan of the apex
of the peak and the integrated ion areas agree with
a library or standard mass spectrum within + 20%;
or, a reverse search yeilds a value equivalent to
the criteria stated above.
b. Samples can be quantitated in two ways. The first
is by the method of standard additions. This
method is always acceptable and should be used
when the exact concentration is needed. The
second method is to be used only for order of
magnitude estimates of concentartion. This is
done by comparing the Total Ion Chromatogram of
the compound in the sample with a standard. For
example, if 100 ng of benzene gives a total of
10,000 counts then a peak corresponding to toluene
with 25,000 counts would be expected to correspond
to about 250 ng. When using this method the
analyst should try to use standards which resemble
the compounds in question as closely as possible.
The internal standard is used as a method check.
For example, if 50 ng of the internal standard
normally gives 5000 integrated area counts this
condition should be met in the sample +20%.
c. Example Calculation
10 gm of solid sample was extracted with methylene
chloride and ethyl ether as in the procedure. The
-------
Revision B 4/15/81 8.27-16
sample lost about 4 gm during the extraction. The
combined extracts were diluted to 500 ml with
methylene chloride. 5 ul was injected with a
split "ratio of 100 to 1. Hexachlorobenzene was
found in the extract with a total of 7,121
total area counts.
Dichlorobenzene was used as a standard
5 ul x 1 mg/ml x 1 ml/1000 ul = 5 ug
Total counts for Dichlorobenzene was 3760
3760 counts/5 ug = 752 counts/ug
Hexachlorobenzene in sample
7121 counts/5 ul x 1 ug/752 counts = 9.47 ug/5 ul
9.47 ug/5 ul x 1000 ul/1 ml x 500 ml = 947000ug
947000 ug = .947 gm
.947 gm/10 gm = .0947 = 9.5% hexachlorobenzene
8. Report
a. Report the results of each analysis giving
each compound identified, the scan number, the
quantity of the compound, and the method used
to calculate that quantity.
b. Example
Compound Quantitation Scan Amount Range
Method #
Hexachloro Estimate/dichloro 693 9.5 % 1-10%
benzene benzene
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Revision B 4/15/81 8.27-17
III. Mixtures of Liquids and Solids
A 10 to 20 gm sample of well mixed waste is used. The sample
is divided into its component phases and the procedures oulined
in sections I and II of this Method are employed for analysis.
A. Separation Procedure for Liquids and Solids
1. Summary
A 10 to 20 gm sample of the waste is separated into
its component phases by centrifugation. The Liquid
Phases are either decanted or pipeted for analysis
using section I and the solid residue is analyzed
using section II.
2. Apparatus and Materials
a. Centrifuge tubes - 10-20 ml pyrex glass or equivalent
with ground glass stopper.
b. Centrifuge - Capable of 2400 RPM
3. Reagents - Reserved
4. Calibration - See calibration sections in parts
I and II of this method
5. Sample Preparation
a. Alliquot a 10 to 20 gm sample of well mixed waste
into a pre weighed cenrifuge tube. Weigh.
b. Place tube into centrifuge and spin at 2400 RPM
for 15 min. or until the solids and liquid phases
are separated.
c. Pour off liquid phase and weigh. Proceed to section
I of this method.
d. Weigh remaining solids and proceed to section II of
this method. The purge and trap method for the
determination of volatiles in solids may be
omitted since the volatiles are determined in the
liquid phase of the sample.
B. Report
1. Report the results as a weighted average of the
liquid phases and solid phase.
2. Example calculation
See sections I and II
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Revision B 4/15/81 8.27-18
Table 8.27-1 (Liquids)
Column: SE-30, SE-52, SE-54 (30 m)
Linear Flow Rate: 50 cm/sec H2 or 30 cm/sec He
Temperature Program: Inject at 25°C then 50°C
Program 50° to 280° C at 8°/min
Hold at 280°C for 15 min.
Table 8.27-2 (Extractables)
Column: SE-30, SE-52, SE-54 (30 m)
Linear Flow Rate: 50 cm/sec H2 or 30 cm/sec He
Temperature Program: Inject at 50°C hold 2 min.
Program to 280°C at 8°C/min
Hold at 280°C for 15 min
Table 8.27-3 (Volatiles)
Column: Same as 8.27-2
Linear Flow Rate: Same as 8.27-2
Temperature Program: Inject at 25 C (cool head of column with
flurocarbon spray) then to 50°C
Program 50°C to 200°C at 4°C/mir
Hold at 200°C for 10 min
-------
H/E. BEF, TOL
BECOHST. GAS CHECHIA HICHAM
DATE:
SAMPLE:
RGC
Benzene Standard
7840 counts
10
CO
H-
0
3
Y
SCAN
TRIE
200
3:20
4CO
6:40
600
10:09
I
800
13:20
cc
M
cc
ISJ
I
Figure 8.27-1
-------
VE. DEF. TOL
BECONST. GAS CHROHATOGRAH
DATE: TIHE:
SAMPLE:
SAMPLE RUN:
CALIB. RUM:
SCANS 100 TO 1809
8B.A. ,
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Revision B 4/15/81 8.56-1
Method 8.56
TOTAL ORGANIC HALIDE
1. Scope and Application
1.1 This method is to be used for the determination of Total Organic
Hal ides as Cl" by carbon adsorption, and requires that all
samples be run in duplicate. Under conditions of duplicate
analysis, the reliable limit of sensitivity 1s 5 ug/L. Organic
halides as used in this method are defined as all organic species
containing chlorine, bromine and Iodine that are adsorbed by
granular activated carbon under the conditions of the method.
Fluorine containing species are not determined by this method.
1.2 This is a microcoulometrlc-titration detection method applicable to
the determination of the compound class listed above in drinking
and ground waters, as provided under 40 CFR 265.92.
1.3 Any modification of this method, beyond those expressly permitted,
shall be considered as major modifications subject to application
and approval of alternate test procedures under 40 CFR 260.21.
1.4 This method is restricted to use by, or under the supervision of,
analysts experienced in the operation of a pyrolys1s/m1crocolumeter
and in the Interpretation of the results.
2. Summary of Method
2.1 A sample of water that has been protected against the loss of
volatiles by the elimination of headspace in the sampling
container, and 1s free of undlssolved solids, is passed through a
column containing 40 mg of activated carbon. The column is washed
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Revision B 4/15/81 8.56-2
to remove any trapped Inorganic halldes, and. 1s. ttien.D.vrolvzed to
convert the adsorbed organohalides to a titratable species that can
be measured by a microcoulometrlc detector.
3. Interferences
3.1 Method Interferences may be caused by contaminants, reagents,
glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free from
Interferences under the conditions of the analysis by running
method blanks.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by treating with chromate
cleaning solution. This should be followed by detergent
washing In hot water. Rinse with tap water and distilled
water, drain dry, and-heat In a muffle furnace at 400°C
for 15 to 30 minutes. Volumetric ware should not be heated
1n a muffle furnace. Glassware should be sealed and stored
in a clean environment after drying and cooling, to prevent
any accumulation of dust or other contaminants.
3.1.2 The use of high purity reagents and gases help to minimize
Interference problems.
3.2 Purity of the activated carbon must be verified before use. Only
carbon samples which register less than 1000 ng/40 mg should be
used. The stock of activated carbon should be stored in its
granular form 1n a glass container with a Teflon seal. Exposure to
the air must be minimized, especially during and after milling and
sieving the activated carbon. No more than a two-week supply
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Revision B 4/15/81 8.56-3
should be prepared in advance. Protect carbon at all times from
all sources of halogenated organic vapors. Store prepared carbon
and packed columns in glass containers with Teflon seals.
3.3 This method is applicable to samples whose, inorganic-halide
concentration does not exceed the organic-halide concentration by
more than 20,000 times.
4. Safety
The toxicity or carcinogenicity of each reagent in this method has not
been precisely defined; however, each chemical compound should be
treated as a potential health hazard. From this viewpoint, exposure to
these chemicals must be reduced to the lowest possible level by whatever
means available. The laboratory is responsible for maintaining a
current-awareness file of OSHA regulations regarding the safe handling
of the chemicals specified in this method. A reference file of
material-handling data sheets should also be made available to all
personnel involved in the chemical analysis.
5. Apparatus and Materials (All specifications are suggested. Catalog
numbers are included for illustration only).
5.1 Sampling equipment, for discrete or composite sampling
5.1.1 Grab-sample bottle - Amber glass, 250-ml, fitted with
Teflon-lined caps. Foil may be substituted for Teflon if
the sample is not corrosive. If amber bottles are not
available, protect samples from light. The container must
be washed and muffled at 400°C before use, to minimize
contamination.
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Revision B 4/15/81 8.56-4
5.2 Adsorption System
5.2.1 Dohrmann Adsorption Module (AD-2), or equivalent,
pressurized, sample and nitrate-wash reservoirs.
5.2.2 Adsorption columns - pyrex, 5 cm long X 6-mm OD X 2-mm ID.
5.2.3 Granular Activated Carbon (GAC) - Filtrasorb-400,
Calgon-APC, or equivalent, ground or milled, and screened to
a 100/200 mesh range. Upon combustion of 40 mg of GAC, the
apparent-haTide background should be 1000-mg Cl"
equivalent or less.
5.2.4 Cerafelt (available from Johns-Manville), or equivalent -
Form this material into plugs using a 2-mrn ID
stainless-steel borer with ejection rod (available from
Dohrmann) to hold 40 mg of GAC in the adsorption columns.
CAUTION: Do not touch this material with your fingers.
5.2.5 Column holders (available from Dohrman).
5.2.6 Volumetric flasks - 100-nt, 50-mL.
A general schematic of the adsorption system is shown in
Figure 1.
5.3 Dohrmann microcoulometric-titration system (MCTS-20 or DX-20), or
equivalent, containing the following components:
5.3.1 Boat sampler.
5.3.2 Pyrolysis furnace.
5.3.3 Microcoulometer with integrator.
5.3.4 Titration cell.
A general description of the analytical system is shown in
Figure 2.
5.4 Strip-Chart Recorder.
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Revision B 4/15/81 8.56-5
6. Reagents
6.1 Sodium sulfite - 0.1 M, ACS reagent grade (12.6 g/L).
6.2 Nitric acid - concentrated.
6.3 Nitrate-Wash Solution (5000 mg NO^/L) - Prepare a nitrate-wash
solution by transferring approximately 8.2 gm of potassium nitrate
into a 1-litre volumetric flask and diluting to volume with reagent
water.
6.4 Carbon dioxide - gas, 99.9% purity.
6.5 Oxygen - 99.9% purity.
6.6 Nitrogen - prepurified.
6.7 7035 Acetic acid in water - Dilute 7 volumes of acetic acid with 3
volumes of water.
6.8 Trichlorophenol solution, stock (1 wL = 10 ug Cl") - Prepare a
stock solution by weighing accurately 1.856 gm of trichlorophenol
into a 100-mL volumetric flask. Dilute to volume with methanol.
6.9 Trichlorophenol solution, calibration (1 uL • 500 ng Cl") -
Dilute 5 ml of the trichlorophenol stock solution to 100 ml with
methanol.
6.10 Trichlorophenol standard, instrument-calibration - First, nitrate
wash a single column packed with 40 mg of activated carbon as
instructed for sample analysis, and then inject the column with
10 yL of the calibration solution.
6.11 Trichlorophenol standard, adsorption-efficiency (100 ug C1"/L) -
Prepare a adsorption-efficiency standard by injecting 10 uL of
stock solution into 1 liter of reagent water.
6.12 Reagent water - Reagent water is defined as a water in which an
-------
Revision B 4/15/81 8.56-6
Interferent 1s not observed at the method detection limit of each
parameter of Interest.
6.13 Blank standard - The reagent water used to prepare the calibration
standard should be used as the blank standard.
7. Calibration
7.1 Check the adsorption efficiency of each newly-prepared batch of
carbon by analyzing 100 ml of the adsorption-efficiency standard,
In duplicate, along with duplicates of the blank standard. The net
recovery should be within 5% of the standard value.
7.2 Nitrate-wash blanks (Method Blanks) - Establish the repeatability
of the method background each day by first analyzing several
nitrate-wash blanks. Monitor this background by spacing nitrate-
wash blanks between each group of eight pyrolysis determinations.
7.2.1 The nitrate-wash blank values are obtained on single columns
packed with 40 mg of activated carbon. Mash with the
nitrate solution as Instructed for sample analysis, and then
pyrolyze the carbon.
7.3 Pyrolyze duplicate Instrument-calibration standards and the blank
standard each day before beginning sample analysis. The net
response to the calibration-standard should be within 3% of the
calibration-standard value. Repeat analysis of the
Instrument-calibration standard after each group of eight pyrolysis
determinations, and before resuming sample analysis after cleaning
or reconditioning the tltration cell or pyrolysis system.
8. Sample Preparation
8.1 Special care should be taken in the handling of the sample to
-------
Revision B 4/15/81 8.56-7
minimize the loss of volatile organohalides. The adsorption
procedure should be performed simultaneously on duplicates.
8.2 Reduce residual chlorine by the addition of sulfite (1 ml of O.-l M
per liter of sample). Addition of sulflte should be done at the
time of sampling 1f the analysis is meant to determine the TOX
concentration at the time of sampling. It should be recognized
that TOX may increase on storage of the sample. Samples should be
stored at 4°C without headspace.
8.3 Adjust pH of the sample to approximately 2 with concentrated HNOj
just prior to adding the sample to the reservoir.
9. Adsorption Procedure
9.1 Connect two columns in series, each containing 40 mg of
100/200-mesh activated carbon.
9.2 Fill the sample reservoir, and pass a metered amount of sample
through the activated-carbon columns at a rate of approximately
3 mL/min. NOTE: 100 ml of sample is the preferred volume for
concentrations of TOX between 5 and 500 ug/L; 50 ml for 501 to 1000
yg/L, and 25 ml for 1001 to 2000 ug/L.
9.3 Wash the co.lumns-1n-series with 2 ml of the 5000-mg/L nitrate
solution at a rate of approximately 2 mL/min to displace Inorganic
chloride ions.
10. Pyrolysis Procedure
10.1 The contents of each column is pyrolyzed separately. After rinsing
with the nitrate solution, the columns should be protected from the
atmosphere and other sources of contamination until ready for
further analysis.
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Revision B 4/15/81 8.56-8
10.2 Pyrolysis of the sample 1s accomplished In two stages. The
volatile components are pyrolyzed 1n a CQg-rich atmosphere at a
low temperature to assure the conversion of brominated
trlhalomethanes to a titratable species. The less volatile
components are then pyrolyzed at a high temperature in an Og-rich
atmosphere.
NOTE: The quartz sampling boat should have been previously muffled
at 800°C for at least 2 to 4 minutes as 1n a previous analysis,
and should be cleaned of any residue by vacuuming.
10.3 Transfer the contents of each column to the quartz boat for
individual analysis.
10.4 If the Dohrmann MC-1 is used for pyrolysis, manual Instructions are
followed for gas flow regulation. If the MCT-20 is used, the
information on the diagram in Figure 3 is used for gas flow
regulation.
10.5 Position the sample for 2 minutes in the 200°C zone of the
pyrolysis tube. For the MCTS-20, the boat 1s positioned just
outside the furnace entrance.
10.6 After 2 minutes, advance the boat Into the 800°C zone (center) of
the pyrolysis furnace. This second and final stage of pyrolysis
may require from 6 to 10 minutes to complete.
11. Detection
The effluent gases are directly analyzed 1n the microcoulometric-titra-
tion cell. Carefully follow manual instructions for optimizing cell
performance.
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Revision B 4/15/81 8.56-9
12. Breakthrough
Because the background bias can be of such an unpredictable nature, it
can be especially difficult to recognize the extent of breakthrough of
organohalides from one column to another. All second-column
measurements for a properly operating system should not exceed
10-percent of the two-column total measurement. If the 10-percent
figure is exceeded, one of three events can have happened. Either the
first column was overloaded and a legitimate measure of breakthrough was
obtained - in which case taking a smaller sample may be necessary; or
channeling or some other failure occurred - in which case the sample may
need to be rerun; or a high, random, bias occurred and the result should
be rejected and the sample rerun. Because knowing which event has
occurred may not be possible, a sample analysis should be repeated often
enough to gain confidence in results. As a general rule, any analyses
that is rejected should be repeated whenever sample is available. In
the event that the second-column measurement is equal to or less than
the nitrate-wash blank value, the second-column value should be
disregarded.
13. Quality Control
13.1 Before performing any analyses, the analyst must demonstrate the
ability to generate acceptable accuracy and precision with this
procedure by the analysis of appropriate quality-control check
samples.
13.2 The laboratory must develop and maintain a statement of method
accuracy for their laboratory. The laboratory should update the
accuracy statement regularly as new recovery measurements are made.
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Revision B 4/15/81 8.56-10
13.3 It is recommended that the laboratory adopt additional
quality-assurance practices for use with this method. The specific
practices that would be most productive will depend upon the needs
of the laboratory and the nature of the samples. Field duplicates
may be analyzed to monitor the precision of the sampling
technique. Whenever possible, the laboratory should perform
analysis of standard reference materials and participate in
relevant performance-evaluation studies.
14. Calculations
OX as Cl~ Is calculated using the following formula:
(cr c3) * (c2 - c3 ). ug/L Total Organ1c Hal1de
5
where:
C-] » ug Cl~ on the first column in series
Cy = U9 Cl" on the second column In series
C., = predetermined, dally, average, method-blank value
(nitrate-wash blank for a 40-mg carbon column)
V = the sample volume In L
15. Accuracy and Precision
These procedures have been applied to a large number of drinking-water
samples. The results of these analysis are summarized in Tables I and
II.
16. Reference
Oressman, R.f Najar, G., Redzikowski, R., paper presented at the
Proceedings of the American Water Works Association Water Quality
Technology Conference, Philadelphia, Dec. 1979.
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Revision B 4/15/81 8.56-11
TABLE I
PRECISION AND ACCURACY DATA FOR MODEL COMPOUNDS
Model
Compound
CHC13
CHBrC12
CHBr2C1
CHBr3
Pentachlorophenol
Sample
A
B
C
Dose Dose Average Standard
wg/L as wg/L C1 % Recovery Deviation
98 88 89 14
160 106 98 9
155 79 86 11
160 67 111 8
120 80 93 9
TABLE II
PRECISION DATA ON TAP WATER ANALYSIS
Avg. halide Standard
ug Cl/L Deviation
71 4.3
94 7.0
191 6.1
No. of
Replicate;
10
11
13
11
7
No. of
Replicates
8
6
4
-------
N2
f
SAMPLE
RESERVOIR
(1 of 4)
NITRATE WASH
RESERVOIR
GAG COLUMN 1
GAC COLUMN 2
50
fO
!-••
in
»-••
O
3
00
Figure 1. Adsorption Schematic
en
\
00
GO
a\
I
M
10
-------
SPARGING
DEVICE
TITRATION
PYROLYSIS
BOAT
INLET
MICROCOULOMETER
WITH INTEGRATOR
STRIP CHART
RECORDER
ADSORPTION
MODULE
Figure 2. CAOX Analysis System Schematic
i—
n>
M-
o
3
03
00
00
•
U1
a\
I
-------
SINGLE BOAT OUTLET
[CONNECT TO
BOAT-INLET
PORTS
IIOiVENT CAPPED
—T "~
PYROLYSIS FURNACE
CO i SO ml/min Oi 100 ml/min
CARRIER OUT REAClANT OUT
o o
"-MD
CO> 10O ml/min
AUXILIARY
OUT
Figure 3. Rear view plumbing schematic for MCTS-20 system.
Valve A is set for first-stage combustion. O2 venting
(push/pull valve out). Port B enters inner combustion
tube: Port C enters outer combustion tube.
H-
01
!-•-
O
D
CD
CO
00
•
UI
ON
I
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Revision B 4/15/81 8.57-1
Method 8.57
Sulfides
1. Scope and Application
1.1 This method is applicable to the measurement of total
and dissolved sulfides in drinking, surface and saline
waters, domestic and industrial wastes.
1.2 Acid insoluble sulfides are not measured by this method.
Copper sulfide is the only common sulfide in this class.
1.3 This method is suitable for the measurement of sulfide
in concentrations above 1 mg/1
2. Summary of Method
2.1 Excess iodine is added to a sample which may or may
not have been treated with zinc acetate to produce zinc
sulfide. The iodine oxidizes the sulfide to sulfur
under acidic conditions. The excess iodine is back
titrated with sodium thiosulfate or phenylarsine oxide.
3. Comments
3.1 Reduced sulfur compounds, such as sulfite, thiosulfate
and hydrosulfite, which decompose in acid may yield erratic
results. Also, volatile iodine-consuming substances
will give high results.
3.2 Samples must be taken with a minimum of aeration.
Sulfide may be volitilized by aeration and any ozygen
inadvertently added to the sample may convert sulfide
to an immeasurable form.
3.3 If the sample is not preserved with zinc acetate, the
analysis must start immediately. Similarly, the
measurement of dissolved sulfides must also be commenced
immediately.
4. Apparatus: Ordinary laboratory glassware
5. Reagents
5.1 Hydrochloric acid, HC1, 6N
5.2 Standard iodine solution, ,0.0250 N: Dissolve 20 to 25 g
KI in a little water in a 'liter volumetric flask and add
3.2 g iodine. Allow to dissolve. Dilute to 1 liter and
standardize against 0.0250 N sodium thiosulfate or
phenylarsine oxide using a starch indicator.
5.3 Phenylarsine oxide 0.0250 N: commercially available.
5.4 Starch indicator: commercially available.
5.5 Procedure for standardization (see Residual Chlorine-
iodometric titration)
6. Procedure
6.1 Unprecipitated sample
6.1.1 Place a known amount of standard iodine solution
(5.2) into a 500 ml flask. The amount should
be estimated to be in excess of the amount of
sulfide expected.
6.1.2 Add distilled water, if necessary, to bring the
volume to approximately 20 ml.
6.1.3 Add 2 ml of 6N HC1 (5.1)
6.1.4 Pipet 200 ml of sample into the flask, keeping
the tip of the pipet below the surface of the
sample.
6.1.5 If the iodine color disappears, add more iodine
O.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
' >0604
-------
Revision B 4/15/81 8.57-2
until the color remains. Record the total
number of milliliters of the standard iodine used
in performing steps 6.1.1 and 6.1.5.
6.1.6 Titrate with reducing solution (0.0250 N sodium
thiosulfate or 0.0250 N phenylarsine oxide
solution (5.3)} using the starch indicator (5.4)
until the blue color disappears. Record the
number of milliliters used.
6.2 Precipitated samples
6.2.1 Add the reagents to the sample in the original
bottle. Perform steps 6.1.1, 6.1.3, 6.1.5, and
6.1.6.
6.3 Dewatered samples
6.3.1 Return the glass fibre filter paper which con-
tains the sample to the. original bottle. Add
200 ml of distilled water. Perform steps* 6.1.1,
6.1.,3, 6.1.5, and 6.1.6.
6.3.2 The calculations (7) should be based on the
original sample put throug the filter.
7. Calculations
7.1 One ml of 0.0250 N standard iodine solution (5.2)
reacts with 0.4 mg of sulfide present in the titration
vessel.
7.2 Use the formula
mg/1 sulfide = 400(A-B)/ml sample
where:
A=ml of 0.0250 N standard iodine solution (5.2)
B=ml of 0.0250 N standard reducing sodium
thiosulfate or phenylarsine oxide solution (5.3)
8. Precision and Accuracy
8.1 Precision and accuracy for this method have not been
determined.
U.S. Environmental Protection Agency
Region V, Library
230 South Dearborn Street
Chicago, Illinois 60604
ana. GOVERNMENT PRINTING OFFICE 1911 Ml-DII/MI 1.1
------- |